EP2316867A1 - Tin-free, aqueous polyurethane dispersions - Google Patents
Tin-free, aqueous polyurethane dispersions Download PDFInfo
- Publication number
- EP2316867A1 EP2316867A1 EP10188971A EP10188971A EP2316867A1 EP 2316867 A1 EP2316867 A1 EP 2316867A1 EP 10188971 A EP10188971 A EP 10188971A EP 10188971 A EP10188971 A EP 10188971A EP 2316867 A1 EP2316867 A1 EP 2316867A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- component
- radiation
- curable
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 229920003009 polyurethane dispersion Polymers 0.000 title claims description 44
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 53
- 239000006185 dispersion Substances 0.000 claims abstract description 53
- 239000002253 acid Substances 0.000 claims abstract description 47
- 229920002635 polyurethane Polymers 0.000 claims abstract description 46
- 239000004814 polyurethane Substances 0.000 claims abstract description 46
- 150000001875 compounds Chemical class 0.000 claims abstract description 37
- JDIBGQFKXXXXPN-UHFFFAOYSA-N bismuth(3+) Chemical class [Bi+3] JDIBGQFKXXXXPN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 25
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000000758 substrate Substances 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 125000003010 ionic group Chemical group 0.000 claims abstract description 11
- 239000004971 Cross linker Substances 0.000 claims abstract description 5
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 5
- 229920003180 amino resin Polymers 0.000 claims abstract description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 41
- -1 bismuth (III) carboxylates Chemical class 0.000 claims description 36
- 229920000728 polyester Polymers 0.000 claims description 23
- 238000000576 coating method Methods 0.000 claims description 21
- 229920000570 polyether Polymers 0.000 claims description 20
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 claims description 14
- 239000008199 coating composition Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- NUMHJBONQMZPBW-UHFFFAOYSA-K bis(2-ethylhexanoyloxy)bismuthanyl 2-ethylhexanoate Chemical compound [Bi+3].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O NUMHJBONQMZPBW-UHFFFAOYSA-K 0.000 claims description 9
- 239000003085 diluting agent Substances 0.000 claims description 9
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 9
- 239000003973 paint Substances 0.000 claims description 9
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- 239000000853 adhesive Substances 0.000 claims description 6
- 230000001070 adhesive effect Effects 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 5
- ANERHPOLUMFRDC-UHFFFAOYSA-K bismuth citrate Chemical compound [Bi+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O ANERHPOLUMFRDC-UHFFFAOYSA-K 0.000 claims description 5
- FNYKAWJEEWSNEH-UHFFFAOYSA-K bismuth;3,3,5,5-tetramethylhexanoate Chemical compound [Bi+3].CC(C)(C)CC(C)(C)CC([O-])=O.CC(C)(C)CC(C)(C)CC([O-])=O.CC(C)(C)CC(C)(C)CC([O-])=O FNYKAWJEEWSNEH-UHFFFAOYSA-K 0.000 claims description 5
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 4
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 claims description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 10
- 239000012948 isocyanate Substances 0.000 abstract description 7
- 150000002513 isocyanates Chemical class 0.000 abstract description 6
- 239000000159 acid neutralizing agent Substances 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 238000010494 dissociation reaction Methods 0.000 abstract 1
- 230000005593 dissociations Effects 0.000 abstract 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 42
- 239000000203 mixture Substances 0.000 description 36
- 239000003054 catalyst Substances 0.000 description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 20
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 18
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 17
- 239000012975 dibutyltin dilaurate Substances 0.000 description 17
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 16
- HGTBAIVLETUVCG-UHFFFAOYSA-N (methylthio)acetic acid Chemical compound CSCC(O)=O HGTBAIVLETUVCG-UHFFFAOYSA-N 0.000 description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 13
- 150000001298 alcohols Chemical class 0.000 description 13
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 11
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 11
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 11
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 10
- 238000003860 storage Methods 0.000 description 10
- FZQMJOOSLXFQSU-UHFFFAOYSA-N 3-[3,5-bis[3-(dimethylamino)propyl]-1,3,5-triazinan-1-yl]-n,n-dimethylpropan-1-amine Chemical compound CN(C)CCCN1CN(CCCN(C)C)CN(CCCN(C)C)C1 FZQMJOOSLXFQSU-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 150000007513 acids Chemical class 0.000 description 9
- 150000001412 amines Chemical class 0.000 description 9
- 239000000470 constituent Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 229920000515 polycarbonate Polymers 0.000 description 9
- 239000004417 polycarbonate Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 8
- 150000002009 diols Chemical class 0.000 description 8
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 8
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 8
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 7
- 239000005058 Isophorone diisocyanate Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 235000011187 glycerol Nutrition 0.000 description 7
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 7
- 238000006386 neutralization reaction Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 6
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 6
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 238000001723 curing Methods 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 6
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 6
- 230000005855 radiation Effects 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000002023 wood Substances 0.000 description 6
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 5
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 5
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 5
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 5
- 238000003848 UV Light-Curing Methods 0.000 description 5
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 150000001621 bismuth Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 5
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 229920000058 polyacrylate Polymers 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 238000006748 scratching Methods 0.000 description 5
- 230000002393 scratching effect Effects 0.000 description 5
- 238000004062 sedimentation Methods 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 4
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 4
- WVQHODUGKTXKQF-UHFFFAOYSA-N 2-ethyl-2-methylhexane-1,1-diol Chemical compound CCCCC(C)(CC)C(O)O WVQHODUGKTXKQF-UHFFFAOYSA-N 0.000 description 4
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 102100026735 Coagulation factor VIII Human genes 0.000 description 4
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 4
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 4
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 4
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 4
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 239000012965 benzophenone Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 description 4
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 4
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 4
- 239000000539 dimer Substances 0.000 description 4
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 4
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 4
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 4
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 239000000600 sorbitol Substances 0.000 description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 4
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 4
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 4
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 3
- PCHXZXKMYCGVFA-UHFFFAOYSA-N 1,3-diazetidine-2,4-dione Chemical group O=C1NC(=O)N1 PCHXZXKMYCGVFA-UHFFFAOYSA-N 0.000 description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 3
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 3
- RDFQSFOGKVZWKF-UHFFFAOYSA-N 3-hydroxy-2,2-dimethylpropanoic acid Chemical compound OCC(C)(C)C(O)=O RDFQSFOGKVZWKF-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Definitions
- the present invention relates to radiation-curable coating compositions based on tin-free, aqueous polyurethane dispersions, to a process for their preparation, to the use of the coating compositions as paints and / or adhesives, and to articles and substrates provided with these paints and / or adhesives.
- aqueous, radiation-curable polyurethane dispersions are synthesized via tin-catalyzed urethanization.
- the principal reason for the catalysis is that in the synthesis of the polyurethane temperatures of 70 ° C may not be significantly exceeded in order to avoid a thermally initiated polymerization of free-radically polymerizable unsaturated groups.
- aliphatic isocyanates which are preferably used in aqueous, radiation-curable polyurethane dispersions, react only very slowly.
- Dibutyltin dilaurate is by far the preferred catalyst for the synthesis of aqueous, radiation-curable polyurethane dispersions due to the high selectivity for the OH-NCO addition and the high catalytic activity.
- Aqueous, radiation-curable polyurethane dispersions prepared with unsuitable catalysts show a coarser particle image, sediment immediately or are significantly more viscous than aqueous, radiation-curable polyurethane dispersions of the same composition, which are catalyzed by DBTL.
- WO 2008148739 Al describes various catalysts which are suitable in principle for the preparation of the polyurethane of an aqueous, radiation-curable polyurethane dispersion.
- DBTL DBTL.
- the object was to provide alternative tin-free polyurethanes for aqueous, radiation-curable polyurethane dispersions to the existing DBTL-catalyzed polyurethanes for aqueous, radiation-curable polyurethane dispersions.
- the properties of the aqueous, radiation-curable polyurethane dispersions should not deviate from those of the synthesized via DBTL catalysis, aqueous, radiation-curable polyurethane dispersions.
- bismuth salts in the presence of acids having a pKa ⁇ 2.5 are outstandingly suitable for synthesizing polyurethane acrylates for aqueous, radiation-curable polyurethane dispersions.
- the polyurethane acrylates for aqueous, radiation-curable polyurethane dispersions catalyzed in this way correspond in their physical and performance properties to the DBTL-catalyzed polyurethane acrylates for aqueous, radiation-curable polyurethane dispersions.
- weight average molecular weight M w of the polyurethane acrylate is an object of a preferred embodiment of this invention to adjust the weight average molecular weight M w of the polyurethane acrylate to a range of 10 3 to 10 6 g / mol.
- weight average molecular weight M w of polyurethane acrylates can be achieved, as they are achieved for DBTL-catalyzed systems.
- the dispersion contains a component (ii), which are reactive diluents which have at least one free-radically polymerizable group.
- (Meth) acrylate in the context of this invention refers to corresponding acrylate or methacrylate functions or to a mixture of both.
- Building component A) and optionally component (ii) are used in amounts such that the content of copolymerizable double bonds is between 0.5 and 6.0, preferably between 1.0 and 5.5, particularly preferably between 1.5 and 5, 0 mol / kg of non-aqueous constituents of the dispersion.
- Component (ii) is used at 0 to 65, preferably 0 to 40, particularly preferably 0 to 35 wt .-%, wherein the wt .-% of components (i) and (ii) add up to 100 wt .-%.
- Component A) contains one or more compounds having at least one isocyanate-reactive group and at least one free-radically polymerizable, unsaturated group.
- Such compounds include, for example, unsaturated group-containing oligomers and polymers such as polyester (meth) acrylates, polyether (meth) acrylates, polyether (meth) acrylates, unsaturated polyester with Allylether Modelltechniken, polyepoxy (meth) acrylates and monomers containing unsaturated groups with a molecular weight ⁇ 700 g / mol and combinations of the compounds mentioned.
- the hydroxyl-containing polyester (meth) acrylates having an OH number in the range from 15 to 300 mg KOH / g substance, preferably from 60 to 200 mg KOH / g substance, are used as component A).
- a total of 7 groups of monomer constituents can be used:
- the first group (a) contains alkanediols or diols or mixtures of these.
- the alkanediols have a molecular weight in the range of 62 to 286 g / mol.
- the alkanediols are preferably selected from the group of ethanediol, 1,2- and 1,3-propanediol, 1,2-, 1,3- and 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, Neopentyl glycol, cyclohexane-1,4-dimethanol, 1,2- and 1,4-cyclohexanediol, 2-ethyl-2-butylpropanediol, ether oxygen-containing diols, such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene, polypropylene or poly
- the second group (b) contains trihydric and higher alcohols having a molecular weight in the range of 92 to 254 g / mol and / or polyethers started on these alcohols.
- Particularly preferred trihydric and higher alcohols are glycerol, trimethylolpropane, pentaerythritol, dipentaerythritol and sorbitol.
- a particularly preferred polyether is the reaction product of 1 mole of trimethylolpropane with 4 moles of ethylene oxide.
- the third group (c) contains monoalcohols.
- Particularly preferred monoalcohols are selected from the group of ethanol, 1- and 2-propanol, 1- and 2-butanol, 1-hexanol, 2-ethylhexanol, cyclohexanol and benzyl alcohol.
- the fourth group (d) contains dicarboxylic acids having a molecular weight in the range of 104 to 600 g / mol and / or their anhydrides.
- Preferred dicarboxylic acids and their anhydrides are selected from the group of phthalic acid, phthalic anhydride, isophthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, cyclohexanedicarboxylic acid, maleic anhydride, fumaric acid, malonic acid, succinic acid, succinic anhydride, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, dodecanedioic acid, hydrogenated Dimers of fatty acids as listed under the sixth group (f).
- the fifth group (e) contains trimellitic acid or trimellitic anhydride.
- the sixth group (f) contains monocarboxylic acids, such as. B. benzoic acid, cyclohexanecarboxylic acid, 2-ethylhexanoic acid, caproic acid, caprylic acid, capric acid, lauric acid, and natural and synthetic fatty acids, such as. Myristic, palmitic, margarine, stearic, beehive, cerotin, palmitoleic, oleic, icosenic, linoleic, linolenic and arachidonic acids.
- monocarboxylic acids such as. B. benzoic acid, cyclohexanecarboxylic acid, 2-ethylhexanoic acid, caproic acid, caprylic acid, capric acid, lauric acid, and natural and synthetic fatty acids, such as. Myristic, palmitic, margarine, stearic, beehive, cerotin, palmitoleic, oleic, ico
- the seventh group (g) contains acrylic acid, methacrylic acid and / or dimeric acrylic acid.
- Suitable hydroxyl-containing polyester (meth) acrylates as component A) comprise the reaction product of at least one constituent from group (a) or (b) with at least one constituent from group (d) or (e) and at least one constituent from group (g).
- Particularly preferred constituents from group (a) are selected from the group of ethanediol, 1,2- and 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexane-1,4-dimethanol, 1,2- and 1,4-cyclohexanediol, 2-ethyl-2-butylpropanediol, ether oxygen-containing diols selected from the group of diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, and tripropylene glycol.
- Preferred constituents from group (b) are selected from the group of glycerol, trimethylolpropane, pentaerythritol or the reaction product of 1 mol of trimethylolpropane with 4 mol of ethylene oxide.
- Particularly preferred components of groups (d) and (e) are selected from the group consisting of phthalic anhydride, isophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, maleic anhydride, fumaric acid, succinic anhydride, glutaric acid, adipic acid, dodecanedioic acid, hydrogenated dimers of fatty acids, such as they are listed under the 6th group (f) and trimellitic anhydride.
- Preferred ingredient from group (g) is acrylic acid.
- dispersing groups generally known from the prior art can also be incorporated into these polyester (meth) acrylates.
- polyethylene glycols and / or methoxypolyethylene glycols may be proportionally used as the alcohol component.
- Alcohol-initiated polyethylene glycols, polypropylene glycols and their block copolymers, and the monomethyl ethers of these polyglycols can be used as compounds.
- Particularly suitable is polyethylene glycol mono-methyl ether having a number average molecular weight Mn in the range of 500 to 1500 g / mol.
- epoxides are the glycidyl ethers of monomeric, oligomeric or polymeric bisphenol A, bisphenol F, hexanediol and / or butanediol or their ethoxylated and / or propoxylated derivatives.
- This reaction can be used in particular to increase the OH number of the polyester (meth) acrylate, since in the epoxide-acid reaction in each case an OH group is formed.
- the acid number of the resulting product is between 0 and 20 mg KOH / g, preferably between 0 and 10 mg KOH / g and more preferably between 0 and 5 mg KOH / g substance.
- the reaction is preferably catalyzed by catalysts such as triphenylphosphine, thiodiglycol, ammonium and / or phosphonium halides and / or zirconium or tin compounds such as tin (II) ethylhexanoate.
- polyester (meth) acrylates is described on page 3, line 25 to page 6, line 24 of DE-A 4 040 290 , on page 5, line 14 to page 11, line 30 of the DE-A 3 316 592 and Page 123 to 135 of PKT Oldring (Ed.) In Chemistry & Technology of UV & EB Formulations For Coatings, Inks & Paints, Vol. 2, 1991, SITA Technology, London on, described.
- hydroxyl-containing polyether (meth) acrylates which arise from the reaction of acrylic acid and / or methacrylic acid with polyethers, such.
- B homopolymers, copolymers or block copolymers of ethylene oxide, propylene oxide and / or tetrahydrofuran on any hydroxy- and / or amine-functional starter molecules, such as.
- B trimethylolpropane, ethylene glycol, propylene glycol, diethylene glycol, Dipropylengykol, glycerol, pentaerythritol, neopentyl glycol, butanediol and hexanediol.
- suitable as component A) are the known hydroxyl-containing epoxy (meth) acrylates having an OH number in the range from 20 to 300 mg KOH / g, preferably from 100 to 280 mg KOH / g, more preferably from 150 to 250 mg KOH / g or hydroxyl-containing polyurethane (meth) acrylates having an OH number in the range of 20 to 300 mg KOH / g, preferably from 40 to 150 mg KOH / g, more preferably from 50 to 140 mg KOH / g.
- Such compounds are also on Page 37 to 56 at PKT Oldring (Ed.), Chemistry & Technology of UV & EB Formulations For Coatings, Inks & Paints, Vol.
- Hydroxyl-containing epoxy (meth) acrylates are based in particular on reaction products of acrylic acid and / or methacrylic acid with epoxides (glycidyl compounds) of monomeric, oligomeric or polymeric bisphenol A, bisphenol F, hexanediol and / or butanediol or their ethoxylated and / or propoxylated derivatives. Hydroxyl-containing epoxy (meth) acrylates also include the addition products of acrylic acid and / or methacrylic acid with epoxides of unsaturated fats (fatty acid triglycerides), such as. B. Photomer® 3005 F (Cognis, Dusseldorf, DE).
- Preferred unsaturated group-containing oligomers and polymers as component A) are compounds selected from the group consisting of polyester (meth) acrylates, polyether (meth) acrylates, polyetherester (meth) acrylates and polyepoxy (meth) acrylates which, in addition to the unsaturated groups, still have hydroxyl groups.
- the unsaturated group-containing monomers having a molecular weight ⁇ 700 g / mol are, for example, 2-hydroxyethyl (meth) acrylate, caprolactone-extended modifications of 2-hydroxyethyl (meth) acrylate such as Pemcure® 12A (Cognis, DE), 2 Hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxy-2,2-dimethylpropyl (meth) acrylate, containing on average monohydroxy-functional di-, tri- or penta (meth) acrylates of polyhydric alcohols, such as trimethylolpropane, Glycerol, pentaerythritol, ditrimethylolpropane, dipentaerythritol, ethoxylated, propoxylated or alkoxylated trimethylolpropane, glycerol, pentaerythritol, ditrimethylolpropane, dip
- alcohols which can be obtained from the reaction of double-bond-containing acids with optionally double-bond-containing, monomeric epoxide compounds can also be used as monohydroxy-functional, (meth) acrylate-containing alcohols.
- Preferred reaction products are selected from the group of (meth) acrylic acid with glycidyl (meth) acrylate or the glycidyl ester tertiary, saturated monocarboxylic acid.
- Tertiary, saturated monocarboxylic acids are, for example, 2,2-dimethylbutyric acid, ethylmethylbutyric, ethylmethylpentane, ethylmethylhexane, ethylmethylheptane and / or ethylmethyloctanoic acid.
- Preferred among the unsaturated group-containing monomers having a molecular weight ⁇ 700 g / mol are 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate and the addition product of Ethylmethylheptankladylester with (meth) acrylic acid and their technical mixtures.
- the compounds listed under component A) can be used alone or as mixtures.
- Component B) contains monomeric mono-, di- and / or triols each having a molecular weight of 32 to 240 g / mol, such as.
- component B) contains oligomeric and / or polymeric, hydroxy-functional compounds.
- oligomeric and / or polymeric, hydroxy-functional compounds include, for example, polyesters, polycarbonates, polyethercarbonate polyols, C2, C3 and / or C4 polyethers, polyetheresters, polycarbonate polyesters having a functionality of from 1.0 to 3.0, each with a weight average the molecular weight M w in the range of 300 to 4000, preferably 500 to 2500 g / mol.
- Hydroxy-functional polyester alcohols are those based on mono-, di- and tricarboxylic acids with monomeric di- and triols, as have already been enumerated as component B), and lactone-based polyester alcohols.
- the carboxylic acids are for example Phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, adipic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, hexahydrophthalic acid, malonic acid, succinic acid, glutaric acid, pimelic acid, suberic acid, sebacic acid, dodecanedioic acid, hydrogenated dimers of the fatty acids and saturated and unsaturated fatty acids such.
- Hydroxy-functional polyetherols are obtainable, for example, by polymerization of cyclic ethers or by reacting alkylene oxides with a starter molecule.
- Hydroxy-functional polycarbonates are hydroxyl-terminated polycarbonates prepared by reacting diols, lactone-modified diols or bisphenols, eg. As bisphenol A, with phosgene or carbonic diesters, such as diphenyl carbonate or dimethyl carbonate, accessible polycarbonates. Hydroxy-functional polyether carbonate polyols are those used for the synthesis of polyurethane dispersions in DE-A 102008000478 to be discribed.
- Component C) comprises compounds having at least one isocyanate-reactive group and additionally at least one hydrophilicizing group.
- Hydrophilizing groups include ionic groups C1) and / or ionic groups C1) resulting from potentially ionic groups C2), the anionic nature C1.1) such as, for example, sulfonium, phosphonium, carboxylate, sulfonate -, phosphonate groups or cationic nature C1.2) such as may be ammonium groups, potentially ionic groups C2), ie Groups which can be converted, for example, by salt formation into ionic groups C1) and / or nonionic groups C3), for example polyether groups, which can be incorporated into the macromolecules by isocyanate-reactive groups.
- suitable isocyanate-reactive groups are hydroxyl and amino groups.
- Compounds containing potentially ionic groups C2) include compounds with potentially anionic groups C2.1) such as mono- and dihydroxycarboxylic acids, mono- and diaminocarboxylic acids, mono- and dihydroxysulfonic acids, mono- and diaminosulfonic acids, mono- and dihydroxyphosphonic acids, mono- and diaminophosphonic acids and / or compounds with potentially cationic groups C2.2), for example ethanolamine, diethanolamine, triethanolamine, 2-propanolamine, dipropanolamine, tripropanolamine, N-methylethanolamine, N-methyldiethanolamine and N, N-dimethylethanolamine.
- potentially anionic groups C2.1 such as mono- and dihydroxycarboxylic acids, mono- and diaminocarboxylic acids, mono- and dihydroxysulfonic acids, mono- and diaminosulfonic acids, mono- and dihydroxyphosphonic acids, mono- and diaminophosphonic acids and / or compounds with potentially cationic groups C2.2
- Preferred compounds containing potentially anionic groups C2.1) are selected from the group consisting of dimethylolpropionic acid, dimethylolbutyric acid, hydroxypivalic acid, N- (2-aminoethyl) alanine, 2- (2-amino-ethylamino) -ethanesulfonic acid, ethylenediamine-propyl- or -butylsulfonic acid, 1,2- or 1,3-propylenediamine-ethylsulfonic acid, 3- (cyclohexylamino) propane 1-sulfonic acid, malic acid, citric acid, glycolic acid, lactic acid, glycine, alanine, taurine, lysine, 3,5-diaminobenzoic acid, an addition product of isophoronediamine (1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, IPDA) and Acrylic acid ( EP-A 916,647 Example 1), the ad
- Particularly preferred compounds containing potentially ionic groups C2) are carboxyl, sulfonic acid and / or tertiary amino-containing compounds such as 2- (2-amino-ethylamino) ethanesulfonic acid, 3- (cyclohexylamino) propane-1-sulfonic acid, the addition product of isophoronediamine and acrylic acid (EP 916 647 A1 , Example 1), hydroxypivalic acid, dimethylolpropionic acid, triethanolamine, tripropanolamine, N-methyl-diethanolamine and / or N, N-dimethylethanolamine.
- component C) contains as compounds with potentially ionic groups hydroxypivalic acid and / or dimethylolpropionic acid.
- Suitable nonionic hydrophilicizing groups C3) are, for example, polyalkylene oxide ethers which contain at least one hydroxyl or amino group and one or more alkylene oxide units, of which at least one is ethylene oxide unit. These polyalkylene oxide ethers are accessible in a manner known per se by alkoxylation of suitable starter molecules.
- starter molecules are saturated monoalcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, the isomers pentanols, hexanols, octanols and nonanols, n-decanol, n-dodecanol, n-tetradecanol, n Hexadecanol, n-octadecanol, cyclohexanol, the isomeric methylcyclohexanols or hydroxymethylcyclohexane, 3-ethyl-3-hydroxymethyloxetane or tetrahydrofurfuryl alcohol, diethylene glycol monoalkyl ethers such as diethylene glycol monobutyl ether, unsaturated alcohols such as allyl alcohol, 1,1-dimethylallyl alcohol or oleic alcohol, di
- trimethylolpropane which is alkoxylated only at one OH group.
- Preferred starter molecules are saturated monoalcohols and trimethylolpropane, which is alkoxylated only at one OH group.
- Diethylene glycol monobutyl ether is particularly preferably used as starter molecule.
- alkylene oxides are, for example, ethylene oxide, 1-butene oxide and propylene oxide, which can be used in any order or in a mixture in the alkoxylation reaction.
- the polyalkylene oxide polyether alcohols are either pure polyethylene oxide polyethers or mixed polyalkylene oxide polyethers whose alkylene oxide units comprise at least 30 mol%, preferably at least 40 mol% ethylene oxide units.
- Preferred nonionic compounds are monofunctional mixed polyalkylene oxide polyethers having at least 40 mole percent ethylene oxide and at most 60 mole percent propylene oxide units.
- trimethylolpropane-started polyalkylene oxides having an OH functionality of 2, such as. B. Tegomer® ® D 3403 (Evonik Industries AG, Essen, DE) and Ymer ® N 120 (Perstorp AB, Sweden).
- the acids mentioned under component C2.1) are converted into the corresponding salts by reaction with neutralizing agents, such as triethylamine, ethyldiisopropylamine, dimethylcyclohexylamine, dimethylethanolamine, ammonia, N-ethylmorpholine, LiOH, NaOH and / or KOH.
- the degree of neutralization is preferably between 50 and 125%.
- the degree of neutralization is defined as follows: in the case of acid-functionalized polymers, the quotient of base and acid; in the case of base-functionalized polymers as quotient of acid and base. If the neutralization is more than 100%, more base is added with acid-functionalized polymers than acid groups are present in the polymer; in the case of base-functionalized polymers, more acid is added than base groups are present in the polymer.
- the bases mentioned under component C2.2) are converted by reaction with neutralizing agents, such as.
- neutralizing agents such as.
- inorganic acids such as hydrochloric acid, phosphoric acid and / or sulfuric acid
- organic acids such as formic acid, acetic acid, lactic acid, methane, ethane and / or p-toluenesulfonic acid, converted into the corresponding salts.
- the degree of neutralization is preferably between 50 and 125%.
- the compounds listed under component C) can also be used in mixtures.
- ionic hydrophilization and the combination of ionic and nonionic hydrophilization are preferred over purely nonionic hydrophilization.
- Component D) are polyisocyanates selected from the group of aromatic, araliphatic, aliphatic or cycloaliphatic polyisocyanates or mixtures of such polyisocyanates.
- Suitable polyisocyanates are, for example, 1,3-cyclohexane diisocyanate, 1-methyl-2,4-diisocyanato-cyclohexane, 1-methyl-2,6-diisocyanato-cyclohexane, tetramethylene diisocyanate, 4,4'-diisocyanatodiphenylmethane, 2,4'-diisocyanatodiphenylmethane, 2,4-diisocyanatotototoluene, 2,6-diisocyanatotoluene, ⁇ , ⁇ , ⁇ ', ⁇ ,' - tetra-methyl-m- or p-xylylene diisocyanate, 1,6-hexamethylene diis
- component E mono- and diamines and / or mono- or difunctional amino alcohols are used as component E).
- Preferred diamines are those which are more reactive towards the isocyanate groups than water, since the extension of the polyester urethane (meth) acrylate optionally takes place in an aqueous medium.
- the diamines are particularly preferably selected from the group of ethylenediamine, 1,6-hexamethylenediamine, isophoronediamine, 1,3-, 1,4-phenylenediamine, piperazine, 4,4'-diphenylmethanediamine, amino-functional polyethylene oxides, amino-functional polypropylene oxides (known by the name Jeffamiri R D series [Huntsman Corp. Europe, Zavantem, Belgium]) and hydrazine. Very particular preference is given to ethylenediamine.
- Preferred monoamines are selected from the group of butylamine, ethylamine and amines of the Jeffamine R M series (Huntsman Corp. Europe, Zavantem, Belgium), amino-functional polyethylene oxides, amino-functional polypropylene oxides and / or amino alcohols.
- bismuth (III) salts are used, such as. Bismuth (III) bromide, bismuth (III) chloride, bismuth (III) fluoride, bismuth (III) iodide, bismuth (III) nitrate, bismuth (III) oxide, bismuth (III) phosphate, bismuth (III) sulfide, Bismuth (III) trifluoromethanesulfonate, bismuth (III) acetate, bismuth (III) neodecanoate, bismuth (III) salicylate, bismuth (III) -2,2,6,6-tetramethyl-3,5-heptanedionate, bismuth (III) 2-ethylhexanoate, bismuth (III) naphthanate (salt of naphthanic acids: on average, C6 to C7 cyclo
- Bismuth (III) carboxylates such as bismuth (III) acetate, bismuth (III) neodecanoate, bismuth (III) salicylate, bismuth (III) -2,2,6,6-tetramethyl-3,5-heptanedionate, bismuth ( III) -2-ethylhexanoate, bismuth (III) naphthanate and bismuth (III) citrate.
- Particularly preferred are bismuth (III) neodecanoate, bismuth (III) 2-ethylhexanoate and bismuth (III) citrate.
- acids G which are used in combination with the bismuth (III) salts, organic and / or inorganic acids having a pKa ⁇ 2.5, preferably ⁇ 2.0 into consideration.
- Suitable acids include, for example, hydrochloric, hydrobromic and iodohydric acid, chloric acid, chloric acid, perchloric acid, iodic acid, periodic acid, perrhric acid, nitric acid, phosphoric acid, phosphorous acid, hypophosphorous acid, diphosphoric acid, selenic acid, selenious acid, sulfurous acid, sulfuric acid, hydrogen sulfates , Thicyanoic acid, methyl, ethyl, n-propyl, n-butyl, dimethyl, di (n-propyl), di (n-butyl), phosphoric (2-ethylhexyl) ester, methanesulfonic acid, p-toluenesulfonic acid, 2,6-dihydroxybenzoic acid, amidosulfonic acid nitroacetic acid, trimethylammoniumacetic acid, dichloro, difluoro-, tribromo, trichloro- and trifluor
- the weight average molecular weight Mw of the polyurethane acrylate (i) can be controlled via the ratio of acid G) to bismuth salt F).
- Bismuth (III) salts are used in terms of the solids content of the aqueous, radiation-curable polyurethane dispersion (amount of the residue after evaporation of all volatile constituents) in amounts of 1 to 30,000 ppm, preferably 10 to 10,000 ppm, more preferably 50 to 1000 ppm.
- the amount of acid used in combination with the bismuth (III) salt refers to the amount of bismuth (III) salt used and is between 10 to 300 mol%, preferably 15 to 150 mol%, particularly preferably 20 to 110 mol%.
- the radiation-curable, aqueous polyurethane acrylates (i) prepared by the process according to the invention have a weight-average molecular weight Mw of 10 3 to 10 6 g / mol, preferably 3 * 10 3 to 9 * 10 5 g / mol, particularly preferably 10 4 to 7 * 10 5 g / mol.
- the determination of the weight-average molecular weight M w of the polyurethane acrylate was carried out by means of gel permeation chromatography using polystyrene as standard and N, N-dimethylacetamide as the mobile phase.
- Component (ii) are reactive diluents, which are compounds which contain at least one free-radically polymerizable group, preferably acrylate and methacrylate groups, and preferably no groups that are reactive toward isocyanate or hydroxy groups.
- Preferred compounds (ii) have 2 to 6, more preferably 4 to 6 (meth) acrylate groups.
- Particularly preferred compounds (ii) have a boiling point of more than 200 ° C at atmospheric pressure.
- Reactive thinner are generally in PKT Oldring (Editor), Chemistry & Technology of UV & EB Formulations for Coatings, Inks & Paints, Vo. II, Chapter III: Reactive Diluents for UV & EB Curable Formulations, Wiley and SITA Technology, London 1997 described.
- Reactive thinners are, for example, the alcohols completely esterified with (meth) acrylic acid, methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 2-propanol, 2-butanol, 2-ethylhexanol, dihydrodicyclopentadienol, tetrahydrofurfuryl alcohol, 3 3,5-trimethylhexanol, octanol, decanol, dodecanol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 2-ethyl-2- butylpropanediol, trimethylpentanediol, 1,3-butylene glycol, 1,
- Component (ii) is preferably selected from the group of (meth) acrylates of tetrols and hexols, such as (meth) acrylates of pentaerythritol, ditrimethylolpropane, dipentaerythritol, sorbitol, ethoxylated, propoxylated or alkoxylated pentaerythritol, ditrimethylolpropane, dipentaerythritol, sorbitol and ethoxylated and or propoxylated derivatives of the alcohols listed and the technical mixtures obtained in the (meth) acrylation of the abovementioned compounds.
- (meth) acrylates of pentaerythritol, ditrimethylolpropane dipentaerythritol, sorbitol, ethoxylated, propoxylated or alkoxylated pentaerythritol, ditrimethylolpropane
- any of the methods known in the art such as emulsifier-shear, acetone, prepolymer-mix, melt-emulsify, ketimine, and solid-spontaneous-dispersing methods, or derivatives thereof, can be used to prepare the dispersions of this invention.
- emulsifier-shear such as emulsifier-shear, acetone, prepolymer-mix, melt-emulsify, ketimine, and solid-spontaneous-dispersing methods, or derivatives thereof.
- the invention also provides a process for preparing radiation-curable, aqueous dispersions based on polyurethane acrylates (i), which comprises reacting components A) to C) in one or more reaction steps with component D) in the presence of components F) and G) a polyurethane acrylate (i) is obtained, wherein a Neutralizing agent for generating the necessary for the dispersion ionic groups before, during or after the preparation of the addition product of A) to D) can be added, followed by a dispersion step by adding water to the addition product of A) to D) or transfer of the addition product from A) to D) in an aqueous template, wherein before, during or after the dispersion a chain extension by means of component E) can take place.
- the invention also provides a process as described above, in which one or more reactive diluents (component (ii)) containing at least one free-radically polymerizable group are added.
- aqueous dispersions based on polyurethane acrylates (i), the components A), B) and C) are introduced into the reactor and optionally diluted with acetone.
- component (ii) may also be added to components A) to C).
- bismuth (III) salt F) and acid G) are added and the mixture is heated to allow the reaction to start. As a rule, temperatures of 30 to 60 ° C are required. Subsequently, the one or more polyisocyanates D) are metered in.
- the reverse variant is also possible, in which case the polyisocyanates D) are introduced and the isocyanate-reactive components A), B) and C) are added.
- the addition of components A), B) and C) can also be carried out successively and in any order.
- a stepwise reaction of the components is possible, that is, the separate reaction of component D) with one or more isocyanate-reactive components A), B) and / or C) before the recovered adduct is further reacted with the unused components.
- the bismuth (III) salt and the acid can also be mixed beforehand and added as a mixture. It is also possible to purify or isolate the metal species which is active from this mixture and to use them as catalyst.
- the isocyanate content is determined at regular intervals by titration, infrared or near-infrared spectroscopy.
- the molar ratios of isocyanate groups in D) to isocyanate-reactive groups in A), B) and C) are from 0.8: 1 to 2.5: 1, preferably 1.2: 1 to 1.5: 1.
- the salt formation of the dispersant takes place acting groups of Komponenete C).
- component C) contains acidic groups are preferred Bases selected from the group of triethylamine, ethyldiisopropylamine, dimethylcyclohexylamine, dimethylethanolamine, ammonia, N-ethylmorpholine, LiOH, NaOH and / or KOH used.
- component C) contains basic groups
- acids selected from the group of lactic acid, acetic acid, phosphoric acid, hydrochloric acid and / or sulfuric acid. If only compounds containing ether groups are used as component C), this neutralization step is omitted.
- a reactive diluent (ii) or a mixture of reactive diluents (ii) may be added.
- the admixing of component (ii) is preferably carried out at 30 to 45 ° C.
- the polyurethane acrylate (i), synthesized from the components A), B), C) and D) in the presence of F) and G), and optionally the reactive diluent (s) (ii), optionally dissolved in acetone, are added with vigorous stirring either into the dispersing water containing the amine (s) E) or, conversely, the mixture is stirred Dispersing water-amine mixture to the polyurethane acrylate solution.
- the dispersions formed in the coating system of the invention are formed.
- the amount of amine E) used depends on the remaining unreacted isocyanate groups.
- the reaction of the still free isocyanate groups with the amine E) can be carried out to 35% to 150%.
- free isocyanate groups react slowly with water.
- unreacted isocyanate groups are no longer present and an amine-functional polyurethane is obtained.
- 80% to 110%, particularly preferably 90% to 100% of the still free isocyanate groups are reacted with the amine E).
- the organic solvent if present, can be distilled off.
- the dispersions then have a solids content of 20 to 60 wt .-%, in particular 30 to 58 wt .-%.
- the invention also relates to the use of the radiation-curable, aqueous dispersions according to the invention for the production of coatings, in particular of paints and adhesives.
- the dispersions according to the invention give clear films after removal of the water by customary methods, such as heat, heat radiation, moving optionally dried air and / or microwaves. Subsequent radiation-chemically and / or free-radically induced crosslinking, the films cure to form high-quality and chemical-resistant lacquer coatings.
- electromagnetic radiation is suitable whose energy, optionally with the addition of suitable photoinitiators, is sufficient to effect a radical polymerization of (meth) acrylate double bonds.
- the radiation-induced polymerization preferably takes place by means of radiation having a wavelength of less than 400 nm, such as UV, electron, X-ray or gamma rays. Particularly preferred is the UV radiation, wherein the curing is initiated with UV radiation in the presence of photoinitiators.
- the photoinitiators a distinction is in principle made between two types, the unimolecular (type I) and the bimolecular (type II).
- Suitable (Type I) systems are aromatic ketone compounds, such as.
- (type II) initiators such as benzoin and its derivatives, benzil ketals, acylphosphine oxides, 2,4,6-trimethyl-benzoyl-diphenylphosphine oxide, bisacylphosphine oxides, phenylglyoxylic acid esters, camphorquinone, ⁇ -aminoalkylphenones, ⁇ , ⁇ -dialkoxyacetophenones and ⁇ -hydroxyalkylphenones , Preference is given to photoinitiators which are easy to incorporate into aqueous coating compositions.
- Such products are, for example, Irgacure® 500 (a mixture of benzophenone and (1-hydroxycyclohexyl) phenylketone, Ciba, Lampertheim, DE), Irgacure® 819 DW (phenylbis- (2,4,6-trimethylbenzoyl) -phosphine oxide, Fa. Ciba, Lampertheim, DE), Esacure® KIP EM (Oligo- [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) -phenyl] -propanone], Lamberti, Aldizzate, Italy). It is also possible to use mixtures of these compounds.
- polar solvents such as.
- acetone and isopropanol can be used.
- the UV curing is carried out at 30 to 70 ° C, because at higher temperature, the degree of conversion of (meth) acrylate groups tends to increase. This can result in better resistance properties.
- a possible temperature sensitivity of the substrate must be taken into account, so that optimum curing conditions for a particular coating agent-substrate combination by the expert in simple preliminary tests are to be determined.
- the radiator (s) which initiate the radical polymerization can be stationary and the coated substrate is moved past the radiator by means of suitable conventional devices, or the radiators are movable by conventional means, so that the coated substrates are stationary during curing. It is also possible to irradiate e.g. in chambers in which the coated substrate is introduced into the chamber, then the radiation is turned on for a certain period, and after the irradiation, the substrate is removed from the chamber again.
- water-soluble peroxides or aqueous emulsions of non-water-soluble initiators are suitable. These radical formers can be combined with accelerators in a known manner.
- aqueous, radiation-curable polyurethane dispersions according to the invention can be applied by the usual techniques to a wide variety of substrates, preferably spraying, rolling, flooding, printing, knife coating, casting, brushing and dipping.
- aqueous, radiation-curable polyurethane dispersions basically all substrates can be coated or coated.
- Preferred substrates are selected from the group consisting of mineral substrates, wood, wood-based materials, furniture, parquet, doors, window frames, metallic objects, plastics, paper, cardboard, cork, mineral substrates, textiles or leather. They are suitable here as a primer and / or as a topcoat.
- the aqueous, radiation-curable polyurethane dispersions of the invention can also be used in or as adhesives, for. B. in contact adhesives, in thermally activated adhesives or in laminating adhesives.
- aqueous, radiation-curable polyurethane dispersions according to the invention can also be used alone or in binder mixtures with other dispersions. These may be dispersions which also contain unsaturated groups, such as. B. unsaturated, polymerizable group-containing dispersions on polyester, polyurethane, polyepoxy (meth) acrylate, polyether, polyamide, polysiloxane, polycarbonate, Epoxyacrylat-, Polyesteracrylat-, polyurethane-polyacrylate and / or polyacrylate.
- unsaturated groups such as. B. unsaturated, polymerizable group-containing dispersions on polyester, polyurethane, polyepoxy (meth) acrylate, polyether, polyamide, polysiloxane, polycarbonate, Epoxyacrylat-, Polyesteracrylat-, polyurethane-polyacrylate and / or polyacrylate.
- dispersions based on polyesters, polyurethanes, polyethers, polyamides, polyvinyl esters, polyvinyl ethers, polysiloxanes, polycarbonates, and / or Polyacrylates to be contained in the coating systems of the invention, the functional groups such as alkoxysilane, hydroxy groups and / or optionally present in blocked form isocyanate groups.
- dual-cure systems can be produced, which can be cured by two different mechanisms.
- the so-called crosslinking agent can furthermore be added to the coating system according to the invention.
- Non-blocked and / or blocked, hydrophilized polyisocyanates for aqueous coating compositions are particularly preferred.
- the coating compositions which comprise the aqueous, radiation-curable polyurethane acrylates according to the invention may also be amino crosslinker resins, melamine- or urea-based and / or polyisocyanates with free or blocked polyisocyanate groups, based on optionally hydrophilicizing polyisocyanates of hexamethylene diisocyanate, isophorone diisocyanate and / or toluylene diisocyanate with urethane , Uretdione, iminoxadiazinedione, isocyanurate, biuret and / or allophanate structures.
- Carbodiimides or polyaziridines are also possible as further crosslinkers.
- the coating compositions according to the invention can with the known in paint technology binders, excipients and additives such.
- pigments dyes or matting agents are added or combined.
- leveling and wetting additives slip additives
- pigments including metallic effect pigments, fillers, nanoparticles, light protection particles, anti-yellowing additives, thickeners and surface tension reduction additives.
- the coating compositions according to the invention are suitable for the coatings of films, wherein a deformation of the coated film takes place between physical drying and UV curing.
- compositions according to the invention for clearcoat applications on wood and plastic substrates, which require good resistance to chemicals after physical drying for blocking resistance and after radiation curing.
- compositions according to the invention for wood and plastics applications with a pigment content ⁇ 10% by weight, based on the total formulation. Should there be an incomplete reaction of the radiation-curable groups in the coating system during radiation curing due to high pigment contents, block-resistant coatings are obtained.
- Coating compositions comprising the radiation-curable aqueous dispersions based on polyurethane acrylate according to the invention and also crosslinkers based on amino resins, blocked polyisocyanates, unblocked polyisocyanates, polyaziridines and / or polycarbodiimides, and / or one or more further dispersions are likewise provided by the present invention.
- substrates coated with the coating compositions of the invention are an object of this invention.
- PSS HEMA 40 50 x 7.8 8 mm Second PSS HEMA 1000; 300 x 7.8 mm Third PSS HEMA 300; 300 x 7.8 mm 4th PSS HEMA 40; 300 x 7.8 mm 5th PSS HEMA 40; 300 x 7.8 mm
- Mobile phase N N-dimethylacetamide flow rate 0.6 ml / min print 100 bar temperature 30 ° C injection volume 100 ⁇ l sample concentration 13.4 g / l default For PSS Polymer Standard Service GmbH, Mainz, DE molecular weight molecular rehearse 162; 374; 1620; 9130; 18100; 32500; 67500; 128000; [G / mol] 246000; 659000; 1000000
- the NCO content was monitored in each case according to DIN 53185 by titration.
- the solids content of the polyurethane dispersion was determined gravimetrically after evaporation of all nonvolatile constituents in accordance with DIN 53216.
- the mean particle size was determined by laser correlation spectroscopy.
- the flow time was determined in accordance with DIN 53211 using the 4 mm DIN cup.
- a sample was stored for 7 days at 40 ° C and then examined for sedimentation, coagulation or serum formation.
- the sample was stable on storage (i.o.) when no changes were observed after storage.
- the gel permeation chromatogram showed a weight average molecular weight M w for the dispersed polyurethane acrylate of 2.00 * 10 5 g / mol.
- Example 2 The following Examples 2) to 18) were carried out analogously to Example 1) but with other catalysts and optionally with the addition of acid.
- example 1) (comparison) 2) (comparison) 3) (comparison) 4) (comparison) Catalyst F) 0.63 g (1.0 mmol) (1.0 mmol) Z Desmorapid Z.
- Examples 2) through 8) show that alternative urethanization catalysts, as known from 2K applications, are not suitable for replacing DBTL in Example 1). This also includes bismuth (III) 2-ethylhexanoate, Example 2). Examples 2), 3), 5) and 8) all had a lower weight-average molecular weight Mw compared to Example 1), consequently a higher MTG and possibly an insufficient storage stability at elevated temperature. Examples 4), 6) and 7) were quite viscous and not very finely divided and did not match the quality of Example 1).
- Examples 9) to 12) according to the invention show that the combination of bismuth (III) 2-ethylhexanoate and the strong acid phosphoric acid di (n-butyl) ester with respect to MTG, ALZ and Mw comparable to Example 1) Results comes.
- Examples 9) to 12) according to the invention show that with the amount of bismuth salt remaining and the amount of acid increasing, the weight-average molecular weight M w of the polyurethane acrylate and the fineness of the aqueous, radiation-curable polyurethane dispersion increase and reach their maximum with equimolar amounts of bismuth salt and acid. If there is an excess of acid compared to the bismuth salt, the weight-average molecular weight Mw decreases again.
- Examples 13) to 15) according to the invention show that other bismuth (III) salts and other strong acids show the same effect as Example 9).
- Examples 16) to 18) show that the addition of a strong acid to stannous 2-ethylhexanoate does not have the same effect as in Examples 9) to 11). The results even show that as the amount of acid increases, the weight average molecular weight M w decreases.
- Desmodur N 3300 trimer with isocyanurate structural units based on hexamethylene diisocyanate, Bayer MaterialScience, Germany
- component D 2.6 g neopentyl glycol
- component B 34.8 g dimethylolpropionic acid
- component C 0.40 g DBTL (0.60 mmol)
- 204.2 g of hydroxyethyl acrylate, component A were metered in so that the temperature did not rise above 65 ° C.
- Example 22 The preparation proceeded according to Example 22), but instead of DBTL 0.40 parts of borochate 24 (0.60 mmol) and 0.13 part of phosphoric acid di (n-butyl) ester (0.60 mmol) were used.
- the gel permeation chromatogram showed a weight average molecular weight M w of 3.31 * 10 3 g / mol.
- Examples 21) and 23) show that the combination of bismuth (III) 2-ethylhexanoate and di (n-butyl) phosphoric acid ester synthesizes almost identical aqueous, radiation-curable polyurethane dispersions in comparison to Examples 20) and 22) can as under DBTL catalysis.
- Example 10 Example 11 (Comparison) (Erf.in) (Erf.in) (Erf.in) (Erf.in) Film transparency 6 , clear coat [A-2] 4-5 5 5 5 5 Storage stability: 50 ° C / 24 h OK OK OK OK OK Storage stability: 40 ° C / 28 d OK OK OK OK OK Water resistance 7 , clearcoat [A-1] 5 5 5 5 Coffee resistance 7, clear coat [A-1] 5 5 5 5 5 5 Ethanol / water (50%) - Resistance, clearcoat [A-1] 5 5 5 5 5 5 Red wine resistance 7 , clearcoat [A-1] 5 5 5 5 Ethanol resistance (98%) 7 , clearcoat [A-1] 4-5 4-5 4-5 Pendulum hardness according to König, clear coat [A-2] after phk.
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Abstract
Description
Die vorliegende Erfindung betrifft strahlungshärtbare Beschichtungsmittel auf der Basis zinnfreier, wässriger Polyurethandispersionen, ein Verfahren zu deren Herstellung, die Verwendung der Beschichtungsmittel als Lacke und / oder Klebstoffe sowie Gegenstände und Substrate versehen mit diesen Lacken und / oder Klebstoffen.The present invention relates to radiation-curable coating compositions based on tin-free, aqueous polyurethane dispersions, to a process for their preparation, to the use of the coating compositions as paints and / or adhesives, and to articles and substrates provided with these paints and / or adhesives.
Bislang werden wässrige, strahlenhärtbare Polyurethandispersionen über zinnkatalysierte Urethanisierung synthetisiert. Der prinzipielle Grund für die Katalyse liegt darin, dass bei der Synthese des Polyurethans Temperaturen von 70 °C nicht wesentlich überschritten werden dürfen, um eine thermisch initiierte Polymerisation der radikalisch polymerisierbaren, ungesättigen Gruppen zu vermeiden. Bei so niedrigen Temperaturen reagieren aliphatische Isocyanate, wie sie bevorzugt in wässrigen, strahlenhärtbaren Polyurethandispersionen verwendet werden, nur sehr langsam. Dibutylzinn-dilaurat (DBTL) ist aufgrund der hohen Selektivität für die OH-NCO-Addition und der hohen katalytischen Aktivität der mit Abstand bevorzugte Katalysator zur Synthese wässriger, strahlenhärtbarer Polyurethandispersionen.So far, aqueous, radiation-curable polyurethane dispersions are synthesized via tin-catalyzed urethanization. The principal reason for the catalysis is that in the synthesis of the polyurethane temperatures of 70 ° C may not be significantly exceeded in order to avoid a thermally initiated polymerization of free-radically polymerizable unsaturated groups. At such low temperatures, aliphatic isocyanates, which are preferably used in aqueous, radiation-curable polyurethane dispersions, react only very slowly. Dibutyltin dilaurate (DBTL) is by far the preferred catalyst for the synthesis of aqueous, radiation-curable polyurethane dispersions due to the high selectivity for the OH-NCO addition and the high catalytic activity.
Für die Katalyse der Urethanisierung sind aus der Lackapplikation von Ein-Komponenten (1K)-und Zwei-Komponenten (2K)-Polyurethandispersionen, d. h. die Umsetzung von hydroxyfunktionalisierten Polyurethandispersionen mit blockierten und nicht blockierten Polyisocyanaten durch Einbrennen auf dem Substrat, verschiedene andere Metall- und NichtMetall-Katalysatoren bekannt, wie z. B. tertiäre Amine, Zinn-, Zink-, Zirkonium-, Kupfer-, Bismuth-, Titan- und Molybdänverbindungen. Diese Katalysatoren sind für die Herstellung von 1K- oder 2K-Lacken optimiert, d. h. sie sollen z. B. ähnliche Topfzeiten und Temperatur-Aktivitätsprofile wie DBTL aufweisen oder die Isocyanat-Alkohol-Reaktion der Isocyanat-Wasser-Reaktion vorziehen. Für die Synthese des Polyurethans einer wässrigen, strahlenhärtbaren Polyurethandispersion sind sie aufgrund von Nebenreaktionen (z. B. Allophanatisierung), geringer katalytischer Aktivität bei für die Synthese von wässrigen, strahlenhärtbaren Polyurethandispersionen typischen Reaktionsbedingungen oder aufgrund der Eigenschaft, dass zu geringe Molekulargewichte erreicht werden, ungeeignet und DBTL deutlich unterlegen.For catalysis of urethanization, paint application of one component (1K) and two component (2K) polyurethane dispersions, i. H. the reaction of hydroxy-functionalized polyurethane dispersions with blocked and unblocked polyisocyanates by baking on the substrate, various other metal and non-metal catalysts known, such. As tertiary amines, tin, zinc, zirconium, copper, bismuth, titanium and molybdenum compounds. These catalysts are optimized for the production of 1K or 2K coatings, i. H. they should z. B. have similar pot lives and temperature activity profiles such as DBTL or prefer the isocyanate-alcohol reaction of the isocyanate-water reaction. For the synthesis of the polyurethane of an aqueous, radiation-curable polyurethane dispersion, they are unsuitable because of side reactions (eg allophanatization), low catalytic activity at reaction conditions typical for the synthesis of aqueous, radiation-curable polyurethane dispersions or due to the property that too low molecular weights are achieved and DBTL clearly inferior.
Wässrige, strahlenhärtbare Polyurethandispersionen, die mit ungeeigneten Katalysatoren hergestellt werden, zeigen ein gröberes Teilchenbild, sedimentieren sofort oder sind deutlich hochviskoser als wässrige, strahlenhärtbare Polyurethandispersionen gleicher Zusammensetzung, die mit DBTL katalysiert werden.Aqueous, radiation-curable polyurethane dispersions prepared with unsuitable catalysts show a coarser particle image, sediment immediately or are significantly more viscous than aqueous, radiation-curable polyurethane dispersions of the same composition, which are catalyzed by DBTL.
Es bestand ein allgemeines Bedürfnis, strahlenhärtbare, wässrige Polyurethandispersionen zur Herstellung von Holzlacken auf neue Lacke umzustellen, die keine Organozinnverbindungen enthalten. Ein repräsentatives Beispiel für eine solche Anforderung sind die geforderten Spezifikationen für Beschichtungen von IKEA in IOS-MAT-066, 2006, S. 4.There has been a general need to convert radiation-curable, aqueous polyurethane dispersions for the production of wood coatings to new coatings that contain no organotin compounds. A representative example of such a requirement is the required specifications for coatings from IKEA in IOS-MAT-066, 2006, p. 4.
Es bestand die Aufgabe, alternative zinnfreie Polyurethane für wässrige, strahlenhärtbare Polyurethandispersionen zu den bestehenden DBTL-katalysierten Polyurethanen für wässrige, strahlenhärtbare Polyurethandispersionen bereitzustellen. Dabei sollen die Eigenschaften der wässrigen, strahlenhärtbaren Polyurethandispersionen nicht von denen der über DBTL-Katalyse synthetisierten, wässrigen, strahlenhärtbaren Polyurethandispersionen abweichen.The object was to provide alternative tin-free polyurethanes for aqueous, radiation-curable polyurethane dispersions to the existing DBTL-catalyzed polyurethanes for aqueous, radiation-curable polyurethane dispersions. In this case, the properties of the aqueous, radiation-curable polyurethane dispersions should not deviate from those of the synthesized via DBTL catalysis, aqueous, radiation-curable polyurethane dispersions.
Überraschender Weise wurde gefunden, dass Bismuthsalze in Gegenwart von Säuren mit einem pKa < 2,5 hervorragend geeignet sind, um Polyurethanacrylate für wässrige, strahlenhärtbare Polyurethandispersionen zu synthetisieren. Die auf diese Weise katalysierten Polyurethanacrylate für wässrige, strahlenhärtbare Polyurethandispersionen entsprechen in den physikalischen und anwendungstechnischen Eigenschaften den DBTL-katalysierten Polyurethanacrylaten für wässrige, strahlenhärtbare Polyurethandispersionen. Weiterhin ist es Aufgabe einer bevorzugten Ausführungsform dieser Erfindung, das Gewichtsmittel des Molekulargewichts Mw des Polyurethanacrylats auf einen Bereich von 103 bis 106 g/mol einzustellen. Dabei können Gewichtsmittel des Molekulargewichts Mw von Polyurethanacrylaten erreicht werden, wie sie für DBTL-katalysierte Systeme erreicht werden.Surprisingly, it has been found that bismuth salts in the presence of acids having a pKa <2.5 are outstandingly suitable for synthesizing polyurethane acrylates for aqueous, radiation-curable polyurethane dispersions. The polyurethane acrylates for aqueous, radiation-curable polyurethane dispersions catalyzed in this way correspond in their physical and performance properties to the DBTL-catalyzed polyurethane acrylates for aqueous, radiation-curable polyurethane dispersions. Furthermore, it is an object of a preferred embodiment of this invention to adjust the weight average molecular weight M w of the polyurethane acrylate to a range of 10 3 to 10 6 g / mol. In this case, weight average molecular weight M w of polyurethane acrylates can be achieved, as they are achieved for DBTL-catalyzed systems.
Die Erfindung betrifft strahlenhärtbare, wässrige Dispersionen auf Basis von Polyurethanacrylaten (i), die dadurch gekennzeichnet sind, dass das Polyurethanacrylat (i) als Aufbaukomponenten
- A) eine oder mehrere Verbindungen mit mindestens einer gegenüber Isocyanat reaktiven Gruppe und mindestens einer radikalisch polymerisierbaren, ungesättigten Gruppe,
- B) eine oder mehrere Verbindungen unterschiedlich von A) mit mindestens einer gegenüber Isocyanat reaktiven Gruppe,
- C) eine oder mehrere Verbindungen mit mindestens einer gegenüber Isocyanat reaktiven Gruppe und zusätzlich mindestens einer hydrophilierend wirkenden Gruppe,
- D) ein oder mehrere organische Polyisocyanate,
- E) gegebenenfalls von A) bis D) verschiedene Verbindungen mit mindestens einer gegenüber Isocyanat reaktiven Gruppe,
enthält, die in Gegenwart von - F) Bismut(III)salz(en) und
- G) einer Säure mit einem pKa < 2,5, bevorzugt < 2,0 als Katalysator umgesetzt werden.
- A) one or more compounds having at least one isocyanate-reactive group and at least one free-radically polymerizable, unsaturated group,
- B) one or more compounds other than A) having at least one isocyanate-reactive group,
- C) one or more compounds having at least one isocyanate-reactive group and additionally at least one hydrophilicizing group,
- D) one or more organic polyisocyanates,
- E) optionally from A) to D) different compounds having at least one isocyanate-reactive group,
contains, in the presence of - F) bismuth (III) salt (s) and
- G) of an acid having a pKa <2.5, preferably <2.0 are reacted as a catalyst.
Optional enthält die Dispersion eine Komponente (ii), wobei es sich um Reaktivverdünner, die mindestens eine radikalisch polymerisierbare Gruppe aufweisen, handelt.Optionally, the dispersion contains a component (ii), which are reactive diluents which have at least one free-radically polymerizable group.
"(Meth)acrylat" bezieht sich im Rahmen dieser Erfindung auf entsprechende Acrylat- oder Methacrylatfunktionen oder auf eine Mischung beider."(Meth) acrylate" in the context of this invention refers to corresponding acrylate or methacrylate functions or to a mixture of both.
Aufbaukomponente A) und gegebenenfalls Komponente (ii) werden dabei in solchen Mengen eingesetzt, dass der Gehalt an copolymerisierbaren Doppelbindungen zwischen 0,5 und 6,0, bevorzugt zwischen 1,0 und 5,5, besonders bevorzugt zwischen 1,5 und 5,0 mol/kg nicht wässriger Bestandteile der Dispersion beträgt.Building component A) and optionally component (ii) are used in amounts such that the content of copolymerizable double bonds is between 0.5 and 6.0, preferably between 1.0 and 5.5, particularly preferably between 1.5 and 5, 0 mol / kg of non-aqueous constituents of the dispersion.
Komponente (ii) wird zu 0 bis 65, bevorzugt 0 bis 40, besonders bevorzugt 0 bis 35 Gew.-% eingesetzt, wobei sich die Gew.-% der Komponenten (i) und (ii) zu 100 Gew.-% addieren.Component (ii) is used at 0 to 65, preferably 0 to 40, particularly preferably 0 to 35 wt .-%, wherein the wt .-% of components (i) and (ii) add up to 100 wt .-%.
Komponente A) enthält eine oder mehrere Verbindungen mit mindestens einer gegenüber Isocyanat reaktiven Gruppe und mindestens einer radikalisch polymerisierbaren, ungesättigten Gruppe. Bei solchen Verbindungen handelt es sich beispielsweise um ungesättigte Gruppen enthaltende Oligomere und Polymere wie Polyester(meth)acrylate, Polyether(meth)acrylate, Polyetherester(meth)acrylate, ungesättigten Polyester mit Allyletherstruktureinheiten, Polyepoxy(meth)acrylate und um ungesättigte Gruppen enthaltende Monomere mit einem Molekulargewicht < 700 g/mol sowie Kombinationen der genannten Verbindungen.Component A) contains one or more compounds having at least one isocyanate-reactive group and at least one free-radically polymerizable, unsaturated group. Such compounds include, for example, unsaturated group-containing oligomers and polymers such as polyester (meth) acrylates, polyether (meth) acrylates, polyether (meth) acrylates, unsaturated polyester with Allyletherstruktureinheiten, polyepoxy (meth) acrylates and monomers containing unsaturated groups with a molecular weight <700 g / mol and combinations of the compounds mentioned.
Von den Polyester(meth)acrylaten werden als Komponente A) die hydroxylgruppenhaltigen Polyester(meth)acrylate mit einer OH-Zahl im Bereich von 15 bis 300 mg KOH/g Substanz, bevorzugt von 60 bis 200 mg KOH/g Substanz eingesetzt. Bei der Herstellung der hydroxyfunktionellen Polyester(meth)acrylate als Komponente A) können insgesamt 7 Gruppen von Monomerbestandteilen zur Anwendung kommen:Of the polyester (meth) acrylates, the hydroxyl-containing polyester (meth) acrylates having an OH number in the range from 15 to 300 mg KOH / g substance, preferably from 60 to 200 mg KOH / g substance, are used as component A). In the production of hydroxyfunctional polyester (meth) acrylates as component A), a total of 7 groups of monomer constituents can be used:
Die erste Gruppe (a) enthält Alkandiole oder Diole oder Gemische dieser. Die Alkandiole weisen ein Molekulargewicht im Bereich von 62 bis 286 g/mol auf. Bevorzugt sind die Alkandiole ausgewählt aus der Gruppe von Ethandiol, 1,2- und 1,3-Propandiol, 1,2-, 1,3- und 1,4-Butandiol, 1,5-Pentandiol, 1,6-Hexandiol, Neopentylglykol, Cyclohexan-1,4-dimethanol, 1,2- und 1,4-Cyclohexandiol, 2-Ethyl-2-butylpropandiol, Ethersauerstoff-enthaltende Diole, wie Diethylenglykol, Triethylenglykol, Tetraethylenglykol, Dipropylenglykol, Tripropylenglykol, Polyethylen-, Polypropylen- oder Polybutylenglykole mit einem Zahlenmittel der Molmassen Mn im Bereich von 200 bis 4000, bevorzugt 300 bis 2000, besonders bevorzugt 450 bis 1200 g/mol. Umsetzungsprodukte der zuvor genannten Diole mit ε-Caprolacton oder anderen Lactonen können ebenfalls als Diole zum Einsatz gelangen.The first group (a) contains alkanediols or diols or mixtures of these. The alkanediols have a molecular weight in the range of 62 to 286 g / mol. The alkanediols are preferably selected from the group of ethanediol, 1,2- and 1,3-propanediol, 1,2-, 1,3- and 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, Neopentyl glycol, cyclohexane-1,4-dimethanol, 1,2- and 1,4-cyclohexanediol, 2-ethyl-2-butylpropanediol, ether oxygen-containing diols, such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene, polypropylene or polybutylene glycols having a number average molecular weight Mn in the range from 200 to 4000, preferably 300 to 2000, particularly preferably 450 to 1200 g / mol. Reaction products of the aforementioned diols with ε-caprolactone or other lactones can also be used as diols.
Die zweite Gruppe (b) enthält drei- und höherwertige Alkohole mit einem Molekulargewicht im Bereich von 92 bis 254 g/mol und /oder auf diesen Alkoholen gestartete Polyether. Besonders bevorzugte drei- und höherwertige Alkohole sind Glycerin, Trimethylolpropan, Pentaerythrit, Dipentaerythrit und Sorbit. Ein besonders bevorzugter Polyether ist das Umsetzungsprodukt von 1 mol Trimethylolpropan mit 4 mol Ethylenoxid.The second group (b) contains trihydric and higher alcohols having a molecular weight in the range of 92 to 254 g / mol and / or polyethers started on these alcohols. Particularly preferred trihydric and higher alcohols are glycerol, trimethylolpropane, pentaerythritol, dipentaerythritol and sorbitol. A particularly preferred polyether is the reaction product of 1 mole of trimethylolpropane with 4 moles of ethylene oxide.
Die dritte Gruppe (c) enthält Monoalkohole. Besonders bevorzugte Monoalkohole sind ausgewählt aus der Gruppe von Ethanol, 1- und 2-Propanol, 1- und 2-Butanol, 1- Hexanol, 2-Ethylhexanol, Cyclohexanol und Benzylalkohol.The third group (c) contains monoalcohols. Particularly preferred monoalcohols are selected from the group of ethanol, 1- and 2-propanol, 1- and 2-butanol, 1-hexanol, 2-ethylhexanol, cyclohexanol and benzyl alcohol.
Die vierte Gruppe (d) enthält Dicarbonsäuren mit einem Molekulargewicht im Bereich von 104 bis 600 g/mol und /oder deren Anhydride. Bevorzugte Dicarbonsäuren und deren Anhydride sind ausgewählt aus der Gruppe von Phthalsäure, Phthalsäureanhydrid, Isophthalsäure, Tetrahydrophthalsäure, Tetrahydrophthalsäureanhydrid, Hexahydrophthalsäure, Hexahydrophthalsäureanhydrid, Cyclohexandicarbonsäure, Maleinsäureanhydrid, Fumarsäure, Malonsäure, Bernsteinsäure, Bernsteinsäureanhydrid, Glutarsäure, Adipinsäure, Pimelinsäure, Korksäure, Sebacinsäure, Dodecandisäure, hydrierte Dimere der Fettsäuren, wie sie unter der sechsten Gruppe (f) aufgelistet sind.The fourth group (d) contains dicarboxylic acids having a molecular weight in the range of 104 to 600 g / mol and / or their anhydrides. Preferred dicarboxylic acids and their anhydrides are selected from the group of phthalic acid, phthalic anhydride, isophthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, cyclohexanedicarboxylic acid, maleic anhydride, fumaric acid, malonic acid, succinic acid, succinic anhydride, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, dodecanedioic acid, hydrogenated Dimers of fatty acids as listed under the sixth group (f).
Die fünfte Gruppe (e) enthält Trimellithsäure oder Trimellithsäureanhydrid.The fifth group (e) contains trimellitic acid or trimellitic anhydride.
Die sechste Gruppe (f) enthält Monocarbonsäuren, wie z. B. Benzoesäure, Cyclohexancarbonsäure, 2-Ethylhexansäure, Capronsäure, Caprylsäure, Caprinsäure, Laurinsäure, und natürliche und synthetische Fettsäuren, wie z. B. Myristin-, Palmitin-, Margarin-, Stearin-, Behen-, Cerotin-, Palmitolein, Öl-, Icosen-, Linol-, Linolen- und Arachidonsäure.The sixth group (f) contains monocarboxylic acids, such as. B. benzoic acid, cyclohexanecarboxylic acid, 2-ethylhexanoic acid, caproic acid, caprylic acid, capric acid, lauric acid, and natural and synthetic fatty acids, such as. Myristic, palmitic, margarine, stearic, beehive, cerotin, palmitoleic, oleic, icosenic, linoleic, linolenic and arachidonic acids.
Die siebte Gruppe (g) enthält Acrylsäure, Methacrylsäure und / oder dimere Acrylsäure.The seventh group (g) contains acrylic acid, methacrylic acid and / or dimeric acrylic acid.
Geeignete hydroxylgruppenhaltige Polyester(meth)acrylate als Komponente A) enthalten das Umsetzungsprodukt von mindestens einem Bestandteil aus Gruppe (a) oder (b) mit mindestens einem Bestandteil aus Gruppe (d) oder (e) und mindestens einem Bestandteil aus Gruppe (g).Suitable hydroxyl-containing polyester (meth) acrylates as component A) comprise the reaction product of at least one constituent from group (a) or (b) with at least one constituent from group (d) or (e) and at least one constituent from group (g).
Besonders bevorzugte Bestandteile aus der Gruppe (a) sind ausgewählt aus der Gruppe von Ethandiol, 1,2- und 1,3-Propandiol, 1,4-Butandiol, 1,6-Hexandiol, Neopentylglykol, Cyclohexan-1,4-dimethanol, 1,2- und 1,4-Cyclohexandiol, 2-Ethyl-2-butylpropandiol, Ethersauerstoff enthaltende Diole, ausgewählt aus der Gruppe von Diethylenglykol, Triethylenglykol, Tetraethylenglykol, Dipropylenglykol, und Tripropylenglykol. Bevorzugte Bestandteile aus der Gruppe (b) sind ausgewählt aus der Gruppe von Glycerin, Trimethylolpropan, Pentaerythrit oder das Umsetzungsprodukt von 1 mol Trimethylolpropan mit 4 mol Ethylenoxid. Besonders bevorzugte Bestandteile aus den Gruppen (d) bzw. (e) sind ausgewählt aus der Gruppe von Phthalsäureanhydrid, Isophthalsäure, Tetrahydrophthalsäureanhydrid, Hexahydrophthalsäure, Hexahydrophthal-säureanhydrid, Maleinsäureanhydrid, Fumarsäure, Bernsteinsäureanhydrid, Glutarsäure, Adipinsäure, Dodecandisäure, hydrierte Dimere der Fettsäuren, wie sie unter der 6. Gruppe (f) aufgelistet sind und Trimellithsäureanhydrid. Bevorzugter Bestandteil aus der Gruppe (g) ist Acrylsäure.Particularly preferred constituents from group (a) are selected from the group of ethanediol, 1,2- and 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexane-1,4-dimethanol, 1,2- and 1,4-cyclohexanediol, 2-ethyl-2-butylpropanediol, ether oxygen-containing diols selected from the group of diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, and tripropylene glycol. Preferred constituents from group (b) are selected from the group of glycerol, trimethylolpropane, pentaerythritol or the reaction product of 1 mol of trimethylolpropane with 4 mol of ethylene oxide. Particularly preferred components of groups (d) and (e) are selected from the group consisting of phthalic anhydride, isophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, maleic anhydride, fumaric acid, succinic anhydride, glutaric acid, adipic acid, dodecanedioic acid, hydrogenated dimers of fatty acids, such as they are listed under the 6th group (f) and trimellitic anhydride. Preferred ingredient from group (g) is acrylic acid.
Gegebenenfalls können in diese Polyester(meth)acrylate auch aus dem Stand der Technik allgemein bekannte, dispergierend wirkende Gruppen eingebaut werden. So können als Alkoholkomponente anteilig Polyethylenglykole und / oder Methoxypolyethylenglykole verwendet werden. Als Verbindungen können auf Alkoholen gestartete Polyethylenglykole, Polypropylenglykole und deren Blockcopolymere sowie die Monomethylether dieser Polyglykole verwendet werden. Besonders geeignet ist Polyethylenglykol-mono-methylether mit einem Zahlenmittel der Molmasse Mn im Bereich von 500 bis 1500 g/mol.Optionally, dispersing groups generally known from the prior art can also be incorporated into these polyester (meth) acrylates. For example, polyethylene glycols and / or methoxypolyethylene glycols may be proportionally used as the alcohol component. Alcohol-initiated polyethylene glycols, polypropylene glycols and their block copolymers, and the monomethyl ethers of these polyglycols can be used as compounds. Particularly suitable is polyethylene glycol mono-methyl ether having a number average molecular weight Mn in the range of 500 to 1500 g / mol.
Weiterhin ist es möglich, nach der Veresterung einen Teil der noch freien, nicht veresterten Carboxylgruppen, insbesondere die der (Meth)acrylsäure, mit Mono-, Di- oder Polyepoxiden umzusetzen. Bevorzugt als Epoxide sind die Glycidylether von monomerem, oligomerem oder polymerem Bisphenol-A, Bisphenol-F, Hexandiol und / oder Butandiol oder deren ethoxylierte und / oder propoxylierte Derivate. Diese Reaktion kann insbesondere zur Erhöhung der OH-Zahl des Polyester(meth)acrylats verwendet werden, da bei der Epoxid-Säure-Reaktion jeweils eine OH-Gruppe entsteht. Die Säurezahl des resultierenden Produkts liegt zwischen 0 und 20 mg KOH/g, bevorzugt zwischen 0 und 10 mg KOH/g und besonders bevorzugt zwischen 0 und 5 mg KOH/g Substanz. Die Reaktion wird bevorzugt durch Katalysatoren wie Triphenylphosphin, Thiodiglykol, Ammonium- und / oder Phosphoniumhalogeniden und / oder Zirkon- oder Zinnverbindungen wie Zinn(II)ethylhexanoat katalysiert.It is also possible, after esterification, to react some of the still free, non-esterified carboxyl groups, in particular those of (meth) acrylic acid, with mono-, di- or polyepoxides. Preferred as epoxides are the glycidyl ethers of monomeric, oligomeric or polymeric bisphenol A, bisphenol F, hexanediol and / or butanediol or their ethoxylated and / or propoxylated derivatives. This reaction can be used in particular to increase the OH number of the polyester (meth) acrylate, since in the epoxide-acid reaction in each case an OH group is formed. The acid number of the resulting product is between 0 and 20 mg KOH / g, preferably between 0 and 10 mg KOH / g and more preferably between 0 and 5 mg KOH / g substance. The reaction is preferably catalyzed by catalysts such as triphenylphosphine, thiodiglycol, ammonium and / or phosphonium halides and / or zirconium or tin compounds such as tin (II) ethylhexanoate.
Die Herstellung von Polyester(meth)acrylaten wird auf der Seite 3, Zeile 25 bis Seite 6, Zeile 24 der
Ebenfalls geeignet als Komponente A) sind hydroxylgruppenhaltige Polyether(meth)acrylate, die aus der Umsetzung von Acrylsäure und / oder Methacrylsäure mit Polyethern hervorgehen, so z. B. Homo-, Co- oder Blockcopolymerisate von Ethylenoxid, Propylenoxid und / oder Tetrahydrofuran auf beliebigen hydroxy- und /oder aminfunktionellen Startermolekülen, wie z. B. Trimethylolpropan, Ethylenglykol, Propylenglykol, Diethylenglykol, Dipropylengykol, Glycerin, Pentaerythrit, Neopentylglykol, Butandiol und Hexandiol.Also suitable as component A) are hydroxyl-containing polyether (meth) acrylates, which arise from the reaction of acrylic acid and / or methacrylic acid with polyethers, such. B. homopolymers, copolymers or block copolymers of ethylene oxide, propylene oxide and / or tetrahydrofuran on any hydroxy- and / or amine-functional starter molecules, such as. B. trimethylolpropane, ethylene glycol, propylene glycol, diethylene glycol, Dipropylengykol, glycerol, pentaerythritol, neopentyl glycol, butanediol and hexanediol.
Ebenfalls geeignet als Komponente A) sind die an sich bekannten hydroxylgruppenhaltigen Epoxy(meth)acrylate mit einer OH-Zahl im Bereich von 20 bis 300 mg KOH/g, bevorzugt von 100 bis 280 mg KOH/g, besonders bevorzugt von 150 bis 250 mg KOH/g oder hydroxylgruppenhaltige Polyurethan(meth)acrylate mit einer OH-Zahl im Bereich von 20 bis 300 mg KOH/g, bevorzugt von 40 bis 150 mg KOH/g, besonders bevorzugt von 50 bis 140 mg KOH/g. Solche Verbindungen werden ebenfalls auf
Bevorzugte ungesättigte Gruppen enthaltende Oligomere und Polymere als Komponente A) sind Verbindungen ausgewählt aus der Gruppe der Polyester(meth)acrylate, Polyether(meth)acrylate, Polyetherester(meth)acrylate undPolyepoxy(meth)acrylate, welche neben den ungesättigten Gruppen noch Hydroxylgruppen aufweisen.Preferred unsaturated group-containing oligomers and polymers as component A) are compounds selected from the group consisting of polyester (meth) acrylates, polyether (meth) acrylates, polyetherester (meth) acrylates and polyepoxy (meth) acrylates which, in addition to the unsaturated groups, still have hydroxyl groups.
Bei den ungesättigte Gruppen enthaltenden Monomeren mit einem Molekulargewicht < 700 g/mol handelt es sich beispielsweise um 2-Hydroxyethyl(meth)acrylat, Caprolacton-verlängerte Modifikationen von 2-Hydroxyethyl(meth)acrylat wie PemcureⓇ 12A (Cognis, DE), 2-Hydroxypropyl-(meth)acrylat, 4-Hydroxybutyl(meth)acrylat, 3-Hydroxy-2,2-dimethylpropyl(meth)acrylat, die im Mittel monohydroxyfunktionellen Di-, Tri- oder Penta(meth)acrylate mehrwertiger Alkohole wie Trimethylolpropan, Glycerin, Pentaerythrit, Ditrimethylolpropan, Dipentaerythrit, ethoxyliertes, propoxyliertes oder alkoxyliertes Trimethylolpropan, Glycerin, Pentaerythrit, Ditrimethylolpropan, Dipentaerythrit oder deren technische Gemische.The unsaturated group-containing monomers having a molecular weight <700 g / mol are, for example, 2-hydroxyethyl (meth) acrylate, caprolactone-extended modifications of 2-hydroxyethyl (meth) acrylate such as Pemcure® 12A (Cognis, DE), 2 Hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxy-2,2-dimethylpropyl (meth) acrylate, containing on average monohydroxy-functional di-, tri- or penta (meth) acrylates of polyhydric alcohols, such as trimethylolpropane, Glycerol, pentaerythritol, ditrimethylolpropane, dipentaerythritol, ethoxylated, propoxylated or alkoxylated trimethylolpropane, glycerol, pentaerythritol, ditrimethylolpropane, dipentaerythritol or their technical mixtures.
Außerdem können auch Alkohole, die sich aus der Umsetzung von doppelbindungshaltigen Säuren mit gegebenenfalls doppelbindungshaltigen, monomeren Epoxidverbindungen erhalten lassen, als monohydroxyfunktionelle, (Meth)acrylatgruppen-haltige Alkohole eingesetzt werden. Bevorzugte Umsetzungsprodukte sind ausgewählt aus der Gruppe von (Meth)acrylsäure mit Glycidyl-(meth)acrylat oder dem Glycidylester tertiärer, gesättigter Monocarbonsäure. Tertiäre, gesättigte Monocarbonsäuren sind beispielsweise 2,2-Dimethylbuttersäure, Ethylmethylbutter-, Ethylmethylpentan-, Ethylmethylhexan-, Ethylmethylheptan- und / oder Ethylmethyloktansäure.In addition, alcohols which can be obtained from the reaction of double-bond-containing acids with optionally double-bond-containing, monomeric epoxide compounds can also be used as monohydroxy-functional, (meth) acrylate-containing alcohols. Preferred reaction products are selected from the group of (meth) acrylic acid with glycidyl (meth) acrylate or the glycidyl ester tertiary, saturated monocarboxylic acid. Tertiary, saturated monocarboxylic acids are, for example, 2,2-dimethylbutyric acid, ethylmethylbutyric, ethylmethylpentane, ethylmethylhexane, ethylmethylheptane and / or ethylmethyloctanoic acid.
Bevorzugt unter den ungesättigte Gruppen enthaltenden Monomeren mit einem Molekulargewicht < 700 g/mol sind 2-Hydroxyethyl(meth)acrylat, 2-Hydroxypropyl(meth)acrylat, Pentaerythrittriacrylat, Dipentaerythritpentaacrylat und das Additionsprodukt aus Ethylmethylheptansäureglycidylester mit (Meth)acrylsäure und deren technische Gemische.Preferred among the unsaturated group-containing monomers having a molecular weight <700 g / mol are 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate and the addition product of Ethylmethylheptansäureglycidylester with (meth) acrylic acid and their technical mixtures.
Die unter Komponente A) aufgezählten Verbindungen können für sich alleine als auch als Mischungen verwendet werden.The compounds listed under component A) can be used alone or as mixtures.
Die Komponente B) enthält monomere Mono-, Di- und/ oder Triole jeweils mit einem Molekulargewicht von 32 bis 240 g/mol, wie z. B. Methanol, Ethanol, 1-Propanol, 1-Butanol, 1-Pentanol, 1-Hexanol, 2-Propanol, 2-Butanol, 2-Ethylhexanol, Ethylenglykol, Diethylenglykol, Triethylenglykol, Tetraethylenglykol, Dipropylenglykol, Tripropylenglykol, 1,2-Propandiol, 1,3-Propandiol, 1,4-Butandiol, Neopentylglykol, 2-Ethyl-2-butylpropandiol, Trimethylpentandiol, 1,3-Butylenglykol, 1,4-Cyclohexandimethanol, 1,6-Hexandiol, 1,2- und 1,4-Cyclohexandiol, hydriertes Bisphenol A (2,2-Bis(4-hydroxycyclohexyl)propan), von Dimerfettsäuren abgeleitete Diole, 2,2-Dimethyl-3-hydroxypropionsäure-(2,2-dimethyl-3-hydroxypropylester), Glycerin, Trimethylolethan, Trimethylolpropan, Trimethylolbutan und / oder Rizinusöl. Bevorzugt sind Neopentylglykol, 1,4-Butandiol, 1,4-Cyclohexandimethanol, 1,6-Hexandiol und / oder Trimethylolpropan.Component B) contains monomeric mono-, di- and / or triols each having a molecular weight of 32 to 240 g / mol, such as. For example, methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 2-propanol, 2-butanol, 2-ethylhexanol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 1,2- Propanediol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 2-ethyl-2-butylpropanediol, trimethylpentanediol, 1,3-butylene glycol, 1,4-cyclohexanedimethanol, 1,6-hexanediol, 1,2- and 1 , 4-cyclohexanediol, hydrogenated bisphenol A (2,2-bis (4-hydroxycyclohexyl) propane), dimer fatty acid derived diols, 2,2-dimethyl-3-hydroxypropionic acid (2,2-dimethyl-3-hydroxypropyl ester), glycerine , Trimethylolethane, trimethylolpropane, trimethylolbutane and / or castor oil. Preference is given to neopentyl glycol, 1,4-butanediol, 1,4-cyclohexanedimethanol, 1,6-hexanediol and / or trimethylolpropane.
Des Weiteren enthält Komponente B) oligomere und / oder polymere, hydroxyfunktionelle Verbindungen. Diese oligomeren und / oder polymeren, hydroxyfunktionellen Verbindungen sind beispielsweise Polyester, Polycarbonate, Polyethercarbonatpolyole, C2-, C 3-, und / oder C4-Polyether, Polyetherester, Polycarbonatpolyester mit einer Funktionalität von 1,0 bis 3,0, jeweils mit einem Gewichtsmittel des Molekulargewichts Mw im Bereich von 300 bis 4000, bevorzugt 500 bis 2500 g/mol.Furthermore, component B) contains oligomeric and / or polymeric, hydroxy-functional compounds. These oligomeric and / or polymeric, hydroxy-functional compounds include, for example, polyesters, polycarbonates, polyethercarbonate polyols, C2, C3 and / or C4 polyethers, polyetheresters, polycarbonate polyesters having a functionality of from 1.0 to 3.0, each with a weight average the molecular weight M w in the range of 300 to 4000, preferably 500 to 2500 g / mol.
Hydroxyfunktionelle Polyesteralkohole sind solche auf Basis von Mono-, Di- und Tricarbonsäuren mit monomeren Di- und Triolen, wie sie bereits als Komponente B) aufgezählt wurden, sowie Polyesteralkohole auf Lacton-Basis. Bei den Carbonsäuren handelt es sich zum Beispiel um Phthalsäure, Isophthalsäure, Terephthalsäure, Trimellithsäure, Adipinsäure, Maleinsäure, Fumarsäure, Tetrahydrophthalsäure, Hexahydrophthalsäure, Malonsäure, Bernsteinsäure, Glutarsäure, Pimelinsäure, Korksäure, Sebacinsäure, Dodecandisäure, hydrierte Dimere der Fettsäuren sowie gesättigte und ungesättige Fettsäuren, wie z. B. Palmitinsäure, Stearinsäure, Myristoleinsäure, Palmitoleinsäure, Ölsäure, Linolsäure, Linolensäure, Rizinolsäure und deren technische Gemische. Von den Di- und Tricarbonsäuren können auch die analogen Anhydride verwendet werden.Hydroxy-functional polyester alcohols are those based on mono-, di- and tricarboxylic acids with monomeric di- and triols, as have already been enumerated as component B), and lactone-based polyester alcohols. The carboxylic acids are for example Phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, adipic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, hexahydrophthalic acid, malonic acid, succinic acid, glutaric acid, pimelic acid, suberic acid, sebacic acid, dodecanedioic acid, hydrogenated dimers of the fatty acids and saturated and unsaturated fatty acids such. As palmitic acid, stearic acid, myristoleic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid and their technical mixtures. Of the di- and tricarboxylic acids, the analog anhydrides can also be used.
Hydroxyfunktionelle Polyetherole sind beispielsweise durch Polymerisation von cyclischen Ethern oder durch Umsetzung von Alkylenoxiden mit einem Startermolekül erhältlich.Hydroxy-functional polyetherols are obtainable, for example, by polymerization of cyclic ethers or by reacting alkylene oxides with a starter molecule.
Hydroxyfunktionelle Polycarbonate sind hydroxyl-terminierte Polycarbonate, die durch Umsetzung von Diolen, Lacton-modifizierten Diolen oder Bisphenolen, z. B. Bisphenol A, mit Phosgen oder Kohlensäurediestern, wie Diphenylcarbonat oder Dimethylcarbonat, zugängliche Polycarbonate. Hydroxyfunktionelle Polyethercarbonatpolyole sind solche, wie sie zum Aufbau von Polyurethandispersionen in
Die Komponente C) umfasst Verbindungen mit mindestens einer gegenüber Isocyanat reaktiven Gruppe und zusätzlich mindestens einer hydrophilierend wirkenden Gruppe.Component C) comprises compounds having at least one isocyanate-reactive group and additionally at least one hydrophilicizing group.
Zu den hydrophilierend wirkenden Gruppen gehören ionische Gruppen C1) und/ oder die aus potentiell ionischen Gruppen C2) hervorgehenden (beispielsweise durch Salzbildung) ionischen Gruppen C1), die anionischer Natur C1.1) wie beispielsweise Sulfonium-, Phosphonium-, Carboxylat-, Sulfonat-, Phosphonat-Gruppen oder kationischer Natur C1.2) wie beispielsweise Ammonium-Gruppen sein können, potentiell ionische Gruppen C2), d.h. Gruppen, die beispielsweise durch Salzbildung in ionische Gruppen C1) überführt werden können und / oder nicht-ionische Gruppen C3) wie beispielsweise Polyethergruppen, die durch isocyanatreaktive Gruppen in die Makromoleküle eingebaut werden können. Bevorzugt geeignete isocyanatreaktive Gruppen sind Hydroxyl- und Aminogruppen.Hydrophilizing groups include ionic groups C1) and / or ionic groups C1) resulting from potentially ionic groups C2), the anionic nature C1.1) such as, for example, sulfonium, phosphonium, carboxylate, sulfonate -, phosphonate groups or cationic nature C1.2) such as may be ammonium groups, potentially ionic groups C2), ie Groups which can be converted, for example, by salt formation into ionic groups C1) and / or nonionic groups C3), for example polyether groups, which can be incorporated into the macromolecules by isocyanate-reactive groups. Preferably suitable isocyanate-reactive groups are hydroxyl and amino groups.
Verbindungen enthaltend potentiell ionische Gruppen C2) umfassen Verbindungen mit potentiell anionischen Gruppen C2.1) wie beispielsweise Mono- und Dihydroxycarbonsäuren, Mono- und Diaminocarbonsäuren, Mono- und Dihydroxysulfonsäuren, Mono- und Diaminosulfonsäuren, Mono- und Dihydroxyphosphonsäuren, Mono- und Diaminophosphonsäuren und/oder Verbindungen mit potentiell kationischen Gruppen C2.2) wie beispielsweise Ethanolamin, Diethanolamin, Triethanolamin, 2-Propanolamin, Dipropanolamin, Tripropanolamin, N-Methylethanolamin, N-Methyl-diethanolamin und N,N-Dimethylethanolamin.Compounds containing potentially ionic groups C2) include compounds with potentially anionic groups C2.1) such as mono- and dihydroxycarboxylic acids, mono- and diaminocarboxylic acids, mono- and dihydroxysulfonic acids, mono- and diaminosulfonic acids, mono- and dihydroxyphosphonic acids, mono- and diaminophosphonic acids and / or compounds with potentially cationic groups C2.2), for example ethanolamine, diethanolamine, triethanolamine, 2-propanolamine, dipropanolamine, tripropanolamine, N-methylethanolamine, N-methyldiethanolamine and N, N-dimethylethanolamine.
Bevorzugte Verbindungen enthaltend potentiell anionischen Gruppen C2.1) sind ausgewählt aus der Gruppe bestehend aus Dimethylolpropionsäure, Dimethylolbuttersäure, Hydroxypivalinsäure, N-(2-Aminoethyl)-alanin, 2-(2-Amino-ethylamino)-ethansulfonsäure, Ethylendiamin-propyl- oder - butylsulfonsäure, 1,2- oder 1,3-Propylendiamin-ethylsulfonsäure, 3-(Cyclohexylamino)propan-1-sulfonsäure, Äpfelsäure, Zitronensäure, Glykolsäure, Milchsäure, Glycin, Alanin, Taurin, Lysin, 3,5-Diaminobenzoesäure, ein Additionsprodukt von Isophorondiamin (1-Amino-3,3,5-trimethyl-5-aminomethylcyclohexan, IPDA) und Acrylsäure (
Besonders bevorzugte Verbindungen enthaltend potentiell ionische Gruppen C2) sind Carboxyl-, Sulfonsäuregruppen und/oder tertiäre Aminogruppen enthaltende Verbindungen wie beispielsweise 2-(2-Amino-ethylamino-)ethansulfonsäure, 3-(Cyclohexylamino)propan-1-sulfonsäure, das Additionsprodukt von Isophorondiamin und Acrylsäure (
Ganz besonders bevorzugt enthält Komponente C) als Verbindungen mit potentiell ionischen Gruppen Hydroxypivalinsäure und / oder Dimethylolpropionsäure.Most preferably, component C) contains as compounds with potentially ionic groups hydroxypivalic acid and / or dimethylolpropionic acid.
Geeignete nicht-ionisch hydrophilierend wirkende Gruppen C3) sind beispielsweise Polyalkylenoxidether, die mindestens eine Hydroxy- oder Aminogruppe, sowie eine oder mehrere Alkylenoxideinheiten, von denen wenigstens eine Ethylenoxideinheit ist, enthalten. Diese Polyalkylenoxidether sind in an sich bekannter Weise durch Alkoxylierung geeigneter Startermoleküle zugänglich.Suitable nonionic hydrophilicizing groups C3) are, for example, polyalkylene oxide ethers which contain at least one hydroxyl or amino group and one or more alkylene oxide units, of which at least one is ethylene oxide unit. These polyalkylene oxide ethers are accessible in a manner known per se by alkoxylation of suitable starter molecules.
Geeignete Startermoleküle sind beispielsweise gesättigte Monoalkohole wie Methanol, Ethanol, n-Propanol, Isopropanol, n-Butanol, Isobutanol, sec-Butanol, die Isomeren Pentanole, Hexanole, Octanole und Nonanole, n-Decanol, n-Dodecanol, n-Tetradecanol, n-Hexadecanol, n-Octadecanol, Cyclohexanol, die isomeren Methylcyclohexanole oder Hydroxymethylcyclohexan, 3-Ethyl-3-hydroxymethyloxetan oder Tetrahydrofurfurylalkohol, Diethylenglykol-monoalkylether wie beispielsweise Diethylenglykolmonobutylether, ungesättigte Alkohole wie Allylalkohol, 1,1-Dimethylallylalkohol oder Oleinalkohol, aromatische Alkohole wie Phenol, die isomeren Kresole oder Methoxyphenole, araliphatische Alkohole wie Benzylalkohol, Anisalkohol oder Zimtalkohol, sekundäre Monoamine wie Dimethylamin, Diethylamin, Dipropylamin, Diisopropylamin, Dibutylamin, Bis-(2-ethylhexyl)-amin, N-Methyl- und N-Ethylcyclohexylamin oder Dicyclohexylamin sowie heterocyclische sekundäre Amine wie Morpholin, Pyrrolidin, Piperidin oder 1H-Pyrazol. Ebenfalls geeignet ist Trimethylolpropan, das nur an einer OH-Gruppe alkoxyliert wird. Bevorzugte Startermoleküle sind gesättigte Monoalkohole und Trimethylolpropan, das nur an einer OH-Gruppe alkoxyliert wird. Besonders bevorzugt wird Diethylenglykolmonobutylether als Startermolekül verwendet.Examples of suitable starter molecules are saturated monoalcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, the isomers pentanols, hexanols, octanols and nonanols, n-decanol, n-dodecanol, n-tetradecanol, n Hexadecanol, n-octadecanol, cyclohexanol, the isomeric methylcyclohexanols or hydroxymethylcyclohexane, 3-ethyl-3-hydroxymethyloxetane or tetrahydrofurfuryl alcohol, diethylene glycol monoalkyl ethers such as diethylene glycol monobutyl ether, unsaturated alcohols such as allyl alcohol, 1,1-dimethylallyl alcohol or oleic alcohol, aromatic alcohols such as phenol, the isomeric cresols or methoxyphenols, araliphatic alcohols such as benzyl alcohol, anisalcohol or cinnamyl alcohol, secondary monoamines such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, bis (2-ethylhexyl) amine, N-methyl- and N-ethylcyclohexylamine or dicyclohexylamine and heterocyclic secondary amines such as morpholine, pyrrolidine, piperidine or 1H-P yrazol. Also suitable is trimethylolpropane, which is alkoxylated only at one OH group. Preferred starter molecules are saturated monoalcohols and trimethylolpropane, which is alkoxylated only at one OH group. Diethylene glycol monobutyl ether is particularly preferably used as starter molecule.
Für die Alkoxylierungsreaktion geeignete Alkylenoxide sind beispielsweise Ethylenoxid, 1-Butenoxid und Propylenoxid, die in beliebiger Reihenfolge oder auch im Gemisch bei der Alkoxylierungsreaktion eingesetzt werden können.For the alkoxylation reaction suitable alkylene oxides are, for example, ethylene oxide, 1-butene oxide and propylene oxide, which can be used in any order or in a mixture in the alkoxylation reaction.
Bei den Polyalkylenoxidpolyetheralkoholen handelt es sich entweder um reine Polyethylenoxidpolyether oder gemischte Polyalkylenoxidpolyether, deren Alkylenoxideinheiten zu mindestens 30 mol-%, bevorzugt zu mindestens 40 mol-% Ethylenoxideinheiten umfassen. Bevorzugte nichtionische Verbindungen sind monofunktionelle gemischte Polyalkylenoxidpolyether, die mindestens 40 mol-% Ethylenoxid- und maximal 60 mol-% Propylenoxideinheiten aufweisen. Ebenfalls bevorzugt sind Trimethylolpropan-gestartete Polyallcylenoxide mit einer OH-Funktionalität von 2, wie z. B. Tegomer® D 3403 (Evonik Industries AG, Essen, DE) und Ymer® N 120 (Perstorp AB, Schweden).The polyalkylene oxide polyether alcohols are either pure polyethylene oxide polyethers or mixed polyalkylene oxide polyethers whose alkylene oxide units comprise at least 30 mol%, preferably at least 40 mol% ethylene oxide units. Preferred nonionic compounds are monofunctional mixed polyalkylene oxide polyethers having at least 40 mole percent ethylene oxide and at most 60 mole percent propylene oxide units. Likewise preferred are trimethylolpropane-started polyalkylene oxides having an OH functionality of 2, such as. B. Tegomer® ® D 3403 (Evonik Industries AG, Essen, DE) and Ymer ® N 120 (Perstorp AB, Sweden).
Die unter Komponente C2.1) genannten Säuren werden durch Umsetzung mit Neutralisationsmitteln, wie Triethylamin, Ethyldiisopropylamin, Dimethylcyclohexylamin, Dimethylethanolamin, Ammoniak, N-Ethylmorpholin, LiOH, NaOH und / oder KOH in die entsprechenden Salze überführt. Der Neutralisationsgrad liegt dabei bevorzugt zwischen 50 und 125%. Der Neutralisationsgrad ist wie folgt definiert: Bei säurefunktionalisierten Polymeren als Quotient aus Base und Säure; bei basefunktionalisierten Polymeren als Quotient aus Säure und Base. Liegt der Neutralisation über 100%, so wird bei säurefunktionalisierten Polymeren mehr Base zugegeben als Säuregruppen im Polymer vorhanden sind; bei basefunktionalisierten Polymeren wird mehr Säure zugegeben als Basegruppen im Polymer vorhanden sind.The acids mentioned under component C2.1) are converted into the corresponding salts by reaction with neutralizing agents, such as triethylamine, ethyldiisopropylamine, dimethylcyclohexylamine, dimethylethanolamine, ammonia, N-ethylmorpholine, LiOH, NaOH and / or KOH. The degree of neutralization is preferably between 50 and 125%. The degree of neutralization is defined as follows: in the case of acid-functionalized polymers, the quotient of base and acid; in the case of base-functionalized polymers as quotient of acid and base. If the neutralization is more than 100%, more base is added with acid-functionalized polymers than acid groups are present in the polymer; in the case of base-functionalized polymers, more acid is added than base groups are present in the polymer.
Die unter Komponente C2.2) genannten Basen werden durch Umsetzung mit Neutralisationsmitteln, wie z. B. anorganische Säuren, wie beispielsweise Salzsäure, Phosphorsäure und / oder Schwefelsäure, und / oder organischen Säuren, wie beispielsweise Ameisensäure, Essigsäure, Milchsäure, Methan-, Ethan- und / oder p-Toluolsulfonsäure, in die entsprechenden Salze überführt. Der Neutralisationsgrad liegt dabei bevorzugt zwischen 50 und 125%.The bases mentioned under component C2.2) are converted by reaction with neutralizing agents, such as. As inorganic acids such as hydrochloric acid, phosphoric acid and / or sulfuric acid, and / or organic acids such as formic acid, acetic acid, lactic acid, methane, ethane and / or p-toluenesulfonic acid, converted into the corresponding salts. The degree of neutralization is preferably between 50 and 125%.
Die unter Komponente C) aufgeführten Verbindungen können auch in Mischungen verwendet werden.The compounds listed under component C) can also be used in mixtures.
Die ionische Hydrophilierung und die Kombination von ionischer und nicht-ionischer Hydrophilierung sind gegenüber der rein nicht-ionischen Hydrophilierung bevorzugt.The ionic hydrophilization and the combination of ionic and nonionic hydrophilization are preferred over purely nonionic hydrophilization.
Die Komponente D) sind Polyisocyanate ausgewählt aus der Gruppe von aromatischen, araliphatischen, aliphatischen oder cycloaliphatischen Polyisocyanaten oder Mischungen solcher Polyisocyanate. Geeignete Polyisocyanate sind beispielsweise 1,3-Cyclohexandiisocyanat, 1-Methyl-2,4-diisocyanato-cyclohexan, 1-Methyl-2,6-düsocyanato-cyclohexan, Tetramethylendiisocyanat, 4,4' - Diisocyanatodiphenylmethan, 2,4' - Diisocyanatodiphenylmethan, 2,4-Diisocyanatotoluol, 2,6-Diisocyanatotoluol, α,α,α',α,'-Tetra-methyl-m- oder p-Xylylendiisocyanat, 1,6-Hexamethylendüsocyanat, 1-Isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexan (Isophorondiisocyanat oder IPDI), 4,4'-Diisocyanato-dicyclohexylmethan, 4-Isocyanatomethyl-1,8-octan-diisocyanat (Triisocyanatononan, TIN) (
Zur Erhöhung des Gewichtsmittel des Molekulargewichts Mw der Polyurethanacrylate werden Mono- und Diamine und / oder mono- oder difunktionelle Aminoalkohole als Komponente E) verwendet. Bevorzugte Diamine sind solche, die gegenüber den Isocyanatgruppen reaktiver sind als Wasser, da die Verlängerung des Polyesterurethan(meth)acrylats gegebenenfalls im wässrigen Medium stattfindet. Besonders bevorzugt sind die Diamine ausgewählt aus der Gruppe von Ethylendiamin, 1,6-Hexamethylendiamin, Isophorondiamin, 1,3-, 1,4-Phenylendiamin, Piperazin, 4,4`-Diphenylmethandiamin, aminofunktionelle Polyethylenoxide, aminofunktionelle Polypropylenoxide (bekannt unter dem Namen JeffamiriⓇ D-Reihe [Huntsman Corp. Europe, Zavantem, Belgien]) und Hydrazin. Ganz besonders bevorzugt ist Ethylendiamin.To increase the weight-average molecular weight M w of the polyurethane acrylates, mono- and diamines and / or mono- or difunctional amino alcohols are used as component E). Preferred diamines are those which are more reactive towards the isocyanate groups than water, since the extension of the polyester urethane (meth) acrylate optionally takes place in an aqueous medium. The diamines are particularly preferably selected from the group of ethylenediamine, 1,6-hexamethylenediamine, isophoronediamine, 1,3-, 1,4-phenylenediamine, piperazine, 4,4'-diphenylmethanediamine, amino-functional polyethylene oxides, amino-functional polypropylene oxides (known by the name Jeffamiri Ⓡ D series [Huntsman Corp. Europe, Zavantem, Belgium]) and hydrazine. Very particular preference is given to ethylenediamine.
Bevorzugte Monoamine sind ausgewählt aus der Gruppe von Butylamin, Ethylamin und Amine der JeffaminⓇ M-Reihe (Huntsman Corp. Europe, Zavantem, Belgien), aminofunktionelle Polyethylenoxide, aminofunktionelle Polypropylenoxide und / oder Aminoalkohole.Preferred monoamines are selected from the group of butylamine, ethylamine and amines of the Jeffamine Ⓡ M series (Huntsman Corp. Europe, Zavantem, Belgium), amino-functional polyethylene oxides, amino-functional polypropylene oxides and / or amino alcohols.
Als Katalysatoren F) für die Urethanisierung zur Herstellung der erfindungsgemäßen strahlenhärtbaren Polyurethandispersionen werden Bismuth(III)salze eingesetzt, wie z. B. Bismuth (III)bromid, Bismuth(III)chlorid, Bismuth(III)fluorid, Bismuth(III)iodid, Bismuth(III)nitrat, Bismuth(III)oxid, Bismuth(III)phosphat, Bismuth(III)sulfid, Bismuth(III)trifluormethansulfonat, Bismuth(III)acetat, Bismuth(III)neodecanoat, Bismuth(III)salicylat, Bismuth(III)-2,2,6,6-tetramethyl-3,5-heptandionat, Bismuth(III)-2-ethylhexanoat, Bismuth(III)naphthanat (Salz von Naphthansäuren: im Durchschnitt C6 bis C7-Cyclocarbonsäuren gewonnen aus einer Naphthafraktion) und Bismuth(III)citrat.As catalysts F) for the urethanization for producing the radiation-curable polyurethane dispersions according to the invention bismuth (III) salts are used, such as. Bismuth (III) bromide, bismuth (III) chloride, bismuth (III) fluoride, bismuth (III) iodide, bismuth (III) nitrate, bismuth (III) oxide, bismuth (III) phosphate, bismuth (III) sulfide, Bismuth (III) trifluoromethanesulfonate, bismuth (III) acetate, bismuth (III) neodecanoate, bismuth (III) salicylate, bismuth (III) -2,2,6,6-tetramethyl-3,5-heptanedionate, bismuth (III) 2-ethylhexanoate, bismuth (III) naphthanate (salt of naphthanic acids: on average, C6 to C7 cyclocarboxylic acids derived from a naphtha fraction) and bismuth (III) citrate.
Bevorzugt eingesetzt werden Bismuth(III)carboxylate wie Bismuth(III)acetat, Bismuth(III)neodecanoat, Bismuth(III)salicylat, Bismuth(III)-2,2,6,6-tetramethyl-3,5-heptandionat, Bismuth(III)-2-ethylhexanoat, Bismuth(III)naphthanat und Bismuth(III)citrat. Besonders bevorzugt sind Bismuth(III)neodecanoat, Bismuth(III)-2-ethylhexanoat und Bismuth(III)citrat.Bismuth (III) carboxylates such as bismuth (III) acetate, bismuth (III) neodecanoate, bismuth (III) salicylate, bismuth (III) -2,2,6,6-tetramethyl-3,5-heptanedionate, bismuth ( III) -2-ethylhexanoate, bismuth (III) naphthanate and bismuth (III) citrate. Particularly preferred are bismuth (III) neodecanoate, bismuth (III) 2-ethylhexanoate and bismuth (III) citrate.
Als Säuren G), die in Kombination mit den Bismuth(III)salzen eingesetzt werden, kommen organische und / oder anorganische Säuren mit einem pKa < 2,5, bevorzugt < 2,0 in Betracht.As acids G), which are used in combination with the bismuth (III) salts, organic and / or inorganic acids having a pKa <2.5, preferably <2.0 into consideration.
Geeignete Säuren sind beispielsweise Chlor-, Brom- und Iod-Wasserstofffsäure, Chlorige Säure, Chlorsäure, Perchlorsäure, Iodsäure, Periodsäure, Perchromsäure, Salpetersäure, Phosphorsäure, Phosphorige Säure, Hypophosphorige Säure, Diphosphorsäure, Selensäure, Selenige Säure, Schweflige Säure, Schwefelsäure, Hydrogensulfate, Thicyansäure, Phosphorsäure-methyl-, -ethyl-, -n-propyl-, -n-butyl-, -dimethyl-, -di-(n-propyl)-, -di-(n-butyl)- und di-(2-ethylhexyl)ester, Methansulfonsäure, p-Toluolsulfonsäure, 2,6-Dihydroxybenzoesäure, Amidosulfonsäure Nitroessigsäure, Trimethylammoniumessigsäure, Dichloro-, Difluoro-, Tribromo-, Trichloro- und Trifluoro-Essigsäure, Malonsäure, Maleinsäure, Bromomaleinsäure, Chloromaleinsäure, Chlorofurmarsäure, Bromofurmarsäure, Oxalsäure, Oxalursäure, Oxanilsäure, 4-Nitrobenzoesäure, protonierte Aminosäuren mit einem pKa < 2,5 und Saccharin.Suitable acids include, for example, hydrochloric, hydrobromic and iodohydric acid, chloric acid, chloric acid, perchloric acid, iodic acid, periodic acid, perrhric acid, nitric acid, phosphoric acid, phosphorous acid, hypophosphorous acid, diphosphoric acid, selenic acid, selenious acid, sulfurous acid, sulfuric acid, hydrogen sulfates , Thicyanoic acid, methyl, ethyl, n-propyl, n-butyl, dimethyl, di (n-propyl), di (n-butyl), phosphoric (2-ethylhexyl) ester, methanesulfonic acid, p-toluenesulfonic acid, 2,6-dihydroxybenzoic acid, amidosulfonic acid nitroacetic acid, trimethylammoniumacetic acid, dichloro, difluoro-, tribromo, trichloro- and trifluoroacetic acid, malonic acid, maleic acid, bromomaleic acid, chloromaleic acid, chlorofurmaric acid, Bromofurmaric acid, oxalic acid, oxaluric acid, oxanilic acid, 4-nitrobenzoic acid, protonated amino acids with a pKa <2.5 and saccharin.
Bevorzugt sind Phosphorsäure-di-(n-butyl)-ester, Methansulfonsäure und p-Toluolsulfonsäure.Preference is given to phosphoric di- (n-butyl) esters, methanesulfonic acid and p-toluenesulfonic acid.
Es wurde überraschenderweise gefunden, dass sich über das Verhältnis von Säure G) zu Bismuthsalz F) das Gewichtsmittel des Molekulargewichts Mw des Polyurethanacrylats (i) steuern lässt.It has surprisingly been found that the weight average molecular weight Mw of the polyurethane acrylate (i) can be controlled via the ratio of acid G) to bismuth salt F).
Bismuth(III)salze werden in Bezug auf den Feststoffgehalt der wässrigen, strahlenhärtbaren Polyurethandispersion (Menge des Rückstandes nach Abdampfen aller flüchtigen Bestandteile) in Mengen von 1 bis 30000 ppm, bevorzugt 10 bis 10000 ppm, besonders bevorzugt 50 bis 1000 ppm eingesetzt. Die Menge an Säure, die in Kombination mit dem Bismuth(III)salz eingesetzt wird, bezieht sich auf die Menge an eingesetztem Bismuth(III)salz und liegt zwischen 10 bis 300 mol%, bevorzugt 15 bis 150 mol%, besonders bevorzugt 20 bis 110 mol%.Bismuth (III) salts are used in terms of the solids content of the aqueous, radiation-curable polyurethane dispersion (amount of the residue after evaporation of all volatile constituents) in amounts of 1 to 30,000 ppm, preferably 10 to 10,000 ppm, more preferably 50 to 1000 ppm. The amount of acid used in combination with the bismuth (III) salt refers to the amount of bismuth (III) salt used and is between 10 to 300 mol%, preferably 15 to 150 mol%, particularly preferably 20 to 110 mol%.
Maximale Gewichtsmittel des Molekulargewichts Mw des Polyurethanacrylats (i) werden erreicht, wenn 100 mol% Säure G) im Verhältnis zum Bismuth(III)salz F) verwendet werden.Maximum weight average molecular weights Mw of the polyurethane acrylate (i) are achieved when 100 mol% acid G) is used in relation to the bismuth (III) salt F).
Die nach dem erfindungsgemäßen Verfahren hergestellten strahlenhärtbaren, wässrigen Polyurethanacrylate (i) weisen ein Gewichtsmittel des Molekulargewichts Mw von 103 bis 106 g/mol, bevorzugt 3*103 bis 9*105 g/mol, besonders bevorzugt 104 bis 7*105 g/mol auf. Die Bestimmung des Gewichtsmittel des Molekulargewichts Mw des Polyurethanacrylats erfolgte mit Hilfe der Gelpermeationschromatographie mit Polystyrol als Standard und N,N-Dimethylacetamid als mobile Phase.The radiation-curable, aqueous polyurethane acrylates (i) prepared by the process according to the invention have a weight-average molecular weight Mw of 10 3 to 10 6 g / mol, preferably 3 * 10 3 to 9 * 10 5 g / mol, particularly preferably 10 4 to 7 * 10 5 g / mol. The determination of the weight-average molecular weight M w of the polyurethane acrylate was carried out by means of gel permeation chromatography using polystyrene as standard and N, N-dimethylacetamide as the mobile phase.
Die Komponente (ii) sind Reaktivverdünner, unter denen Verbindungen zu verstehen sind, die mindestens eine radikalisch polymerisierbare Gruppe, bevorzugt Acrlyat- und Methacrylatgruppen, und bevorzugt keine gegenüber Isocyanat- oder Hydroxygruppen reaktiven Gruppen enthalten. Bevorzugte Verbindungen (ii) weisen 2 bis 6, besonders bevorzugt 4 bis 6 (Meth)acrylatgruppen auf.Component (ii) are reactive diluents, which are compounds which contain at least one free-radically polymerizable group, preferably acrylate and methacrylate groups, and preferably no groups that are reactive toward isocyanate or hydroxy groups. Preferred compounds (ii) have 2 to 6, more preferably 4 to 6 (meth) acrylate groups.
Besonders bevorzugte Verbindungen (ii) weisen einen Siedepunkt von mehr als 200 °C bei Normaldruck auf.Particularly preferred compounds (ii) have a boiling point of more than 200 ° C at atmospheric pressure.
Reaktiwerdünner sind allgemein in
Reaktiwerdünner sind beispielsweise die mit (Meth)acrylsäure vollständig veresterten Alkohole Methanol, Ethanol, 1-Propanol, 1-Butanol, 1-Pentanol, 1-Hexanol, 2-Propanol, 2-Butanol, 2-Ethylhexanol, Dihydrodicyclopentadienol, Tetrahydrofurfurylalkohol, 3,3,5-Trimethylhexanol, Octanol, Decanol, Dodecanol, Ethylenglykol, Diethylenglykol, Triethylenglykol, Tetraethylenglykol, Dipropylenglykol, Tripropylenglykol, 1,2-Propandiol, 1,3-Propandiol, 1,4-Butandiol, Neopentylglykol, 2-Ethyl-2-butylpropandiol, Trimethylpentandiol, 1,3-Butylenglykol, 1,4-Cyclohexandimethanol, 1,6-Hexandiol, 1,2- und 1,4-Cyclohexandiol, hydriertes Bisphenol A (2,2-Bis(4-hydroxycyclohexyl)propan), Glycerin, Trimethylolethan, Trimethylolpropan Trimethylolbutan, Pentaerythrit, Ditrimethylolpropan, Dipentaerythrit, Sorbitol sowie ethoxylierte und / oder propoxylierte Derivate der aufgeführten Alkohole und die bei der (Meth)acrylierung der vorgenannten Verbindungen anfallenden technischen Gemische.Reactive thinners are, for example, the alcohols completely esterified with (meth) acrylic acid, methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 2-propanol, 2-butanol, 2-ethylhexanol, dihydrodicyclopentadienol, tetrahydrofurfuryl alcohol, 3 3,5-trimethylhexanol, octanol, decanol, dodecanol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 2-ethyl-2- butylpropanediol, trimethylpentanediol, 1,3-butylene glycol, 1,4-cyclohexanedimethanol, 1,6-hexanediol, 1,2- and 1,4-cyclohexanediol, hydrogenated bisphenol A (2,2-bis (4-hydroxycyclohexyl) propane), Glycerol, trimethylolethane, trimethylolpropane trimethylolbutane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, sorbitol and ethoxylated and / or propoxylated derivatives of the alcohols listed and the resulting in the (meth) acrylation of the aforementioned compounds technical mixtures.
Die Komponente (ii) ist bevorzugt ausgewählt aus der Gruppe von (Meth)acrylaten von Tetrolen und Hexolen, wie (Meth)acrylate von Pentaerythrit, Ditrimethylolpropan, Dipentaerythrit, Sorbitol, ethoxyliertes, propoxyliertes oder alkoxyliertes Pentaerythrit, Ditrimethylolpropan, Dipentaerythrit, Sorbitol sowie ethoxylierte und / oder propoxylierte Derivate der aufgeführten Alkohole und die bei der (Meth)acrylierung der vorgenannten Verbindungen anfallenden technischen Gemische.Component (ii) is preferably selected from the group of (meth) acrylates of tetrols and hexols, such as (meth) acrylates of pentaerythritol, ditrimethylolpropane, dipentaerythritol, sorbitol, ethoxylated, propoxylated or alkoxylated pentaerythritol, ditrimethylolpropane, dipentaerythritol, sorbitol and ethoxylated and or propoxylated derivatives of the alcohols listed and the technical mixtures obtained in the (meth) acrylation of the abovementioned compounds.
Zur Herstellung der erfindungsgemäßen Dispersionen können sämtliche, aus dem Stand der Technik bekannte Verfahren wie Emulgator-Scherkraft-, Aceton-, Präpolymer-Misch-, Schmelz-Emulgier-, Ketimin- und Feststoff-Spontan-Dispergier-Verfahren oder Abkömmlinge davon verwendet werden. Eine Zusammenfassung dieser Methoden findet sich in
Gegenstand der Erfindung ist auch ein Verfahren zur Herstellung strahlenhärtbarer, wässriger Dispersionen auf Basis von Polyurethanacrylaten (i), dadurch gekennzeichnet, dass durch Umsetzen der Komponenten A) bis C) in einem oder mehreren Reaktionsschritten mit Komponente D) in Gegenwart von Komponenten F) und G) ein Polyurethanacrylat (i) erhalten wird, wobei ein Neutralisationsmittel zur Erzeugung der für die Dispergierung notwendigen ionischen Gruppen vor, während oder nach der Herstellung des Additionsproduktes von A) bis D) zugegeben werden kann, gefolgt von einem Dispergierschritt durch Zugabe von Wasser zum Additionsprodukt von A) bis D) bzw. Überführen des Additionsproduktes von A) bis D) in eine wässrige Vorlage, wobei vor, während oder nach der Dispergierung eine Kettenverlängerung mittels Komponente E) erfolgen kann.The invention also provides a process for preparing radiation-curable, aqueous dispersions based on polyurethane acrylates (i), which comprises reacting components A) to C) in one or more reaction steps with component D) in the presence of components F) and G) a polyurethane acrylate (i) is obtained, wherein a Neutralizing agent for generating the necessary for the dispersion ionic groups before, during or after the preparation of the addition product of A) to D) can be added, followed by a dispersion step by adding water to the addition product of A) to D) or transfer of the addition product from A) to D) in an aqueous template, wherein before, during or after the dispersion a chain extension by means of component E) can take place.
Gegenstand der Erfindung ist auch ein Verfahren gemäß vorstehender Beschreibung, bei dem ein oder mehrere Reaktiwerdünner (Komponente (ii)), der mindestens eine radikalisch polymerisierbare Gruppe enthält, beigemischt werden.The invention also provides a process as described above, in which one or more reactive diluents (component (ii)) containing at least one free-radically polymerizable group are added.
Zur Herstellung strahlenhärtbarer, wässriger Dispersionen auf Basis von Polyurethanacrylaten (i) werden die Komponenten A), B) und C) im Reaktor vorgelegt und gegebenenfalls mit Aceton verdünnt. Gegebenenfalls kann auch Komponente (ii) zu den Komponenten A) bis C) zugesetzt werden. Zur Katalyse der Addition an das Polyisocyanat D) werden Bismuth(III)salz F) und Säure G) zugesetzt und die Mischung erwärmt, um ein Anspringen der Reaktion zu ermöglichen. In der Regel sind dazu Temperaturen von 30 bis 60 °C nötig. Anschließend dosiert man das oder die Polyisocyanate D) zu. Auch die umgekehrte Variante ist möglich, wobei dann die Polyisocyanate D) vorgelegt und die isocyanatreaktiven Komponenten A), B) und C) zugegeben werden. Die Zugabe der Komponenten A), B) und C) kann auch nacheinander und in beliebiger Reihenfolge erfolgen. Ebenfalls ist eine stufenweise Umsetzung der Komponenten möglich, das heißt die separate Umsetzung von Komponente D) mit einer oder mehreren isocyanatreaktiven Komponenten A), B) und / oder C) bevor das gewonnene Addukt mit den noch nicht verwendeten Komponenten weiter umgesetzt wird.For the preparation of radiation-curable, aqueous dispersions based on polyurethane acrylates (i), the components A), B) and C) are introduced into the reactor and optionally diluted with acetone. Optionally, component (ii) may also be added to components A) to C). To catalyze the addition to the polyisocyanate D) bismuth (III) salt F) and acid G) are added and the mixture is heated to allow the reaction to start. As a rule, temperatures of 30 to 60 ° C are required. Subsequently, the one or more polyisocyanates D) are metered in. The reverse variant is also possible, in which case the polyisocyanates D) are introduced and the isocyanate-reactive components A), B) and C) are added. The addition of components A), B) and C) can also be carried out successively and in any order. Also, a stepwise reaction of the components is possible, that is, the separate reaction of component D) with one or more isocyanate-reactive components A), B) and / or C) before the recovered adduct is further reacted with the unused components.
Statt der Kombination aus Bismuth(III)salz und Säure können auch zuvor das Bismuth(III)salz und die Säure gemischt und als Mischung zugegeben werden. Ebenfalls ist es möglich, die aus dieser Mischung aktive Metallspezies aufzureinigen bzw. zu isolieren und diese als Katalysator zu verwenden.Instead of the combination of bismuth (III) salt and acid, the bismuth (III) salt and the acid can also be mixed beforehand and added as a mixture. It is also possible to purify or isolate the metal species which is active from this mixture and to use them as catalyst.
Zur Kontrolle der Reaktion wird der Isocyanatgehalt in regelmäßigen Abständen über Titration, Infrarot- oder Nahinfrarot-Spektroskopie, bestimmt.To control the reaction, the isocyanate content is determined at regular intervals by titration, infrared or near-infrared spectroscopy.
Die molaren Verhältnisse von Isocyanatgruppen in D) zu gegenüber Isocyanat reaktiven Gruppen in A), B) und C) betragen von 0,8 : 1 bis 2,5 : 1, bevorzugt 1,2 : 1 bis 1,5 : 1.The molar ratios of isocyanate groups in D) to isocyanate-reactive groups in A), B) and C) are from 0.8: 1 to 2.5: 1, preferably 1.2: 1 to 1.5: 1.
Nach der Herstellung des Polyurethanacrylats (i) nach dem erfindungsgemäßen Verfahren aus den Komponenten A), B), C) und D) in Gegenwart von F) und G) erfolgt, falls dies noch nicht in den Ausgangsmolekülen durchgeführt wurde, die Salzbildung der dispergierend wirkenden Gruppen der Komponenete C). Im Fall, dass Komponente C) saure Gruppen enthält, werden bevorzugt Basen ausgewählt aus der Gruppe von Triethylamin, Ethyldiisopropylamin, Dimethylcyclohexylamin, Dimethylethanolamin, Ammoniak, N-Ethylmorpholin, LiOH, NaOH und / oder KOH eingesetzt. Im Fall, dass Komponente C) basische Gruppen enthält, werden bevorzugt Säuren ausgewählt aus der Gruppe von Milchsäure, Essigsäure, Phosphorsäure, Chlorwasserstoffsäure und / oder Schwefelsäure eingesetzt. Werden als Komponente C) nur Ethergruppen enthaltende Verbindungen eingesetzt, entfällt dieser Neutralisationsschritt.After preparation of the polyurethane acrylate (i) by the process according to the invention from the components A), B), C) and D) in the presence of F) and G), if this has not yet been carried out in the starting molecules, the salt formation of the dispersant takes place acting groups of Komponenete C). In case component C) contains acidic groups are preferred Bases selected from the group of triethylamine, ethyldiisopropylamine, dimethylcyclohexylamine, dimethylethanolamine, ammonia, N-ethylmorpholine, LiOH, NaOH and / or KOH used. In the case where component C) contains basic groups, preference is given to using acids selected from the group of lactic acid, acetic acid, phosphoric acid, hydrochloric acid and / or sulfuric acid. If only compounds containing ether groups are used as component C), this neutralization step is omitted.
Im Anschluss kann optional ein Reaktiwerdünner (ii) oder einer Mischung von Reaktivverdünnern (ii) zugegeben werden. Das Zumischen von Komponente (ii) erfolgt bevorzugt bei 30 bis 45 °C. Sobald diese sich gelöst hat, folgt gegebenenfalls der letzte Reaktionsschritt, bei dem im wässrigen Medium eine Molekulargewichtserhöhung und die Ausbildung der für das erfindungsgemäße Beschichtungssystem benötigten Dispersionen stattfinden: Das Polyurethanacrylat (i), synthetisiert aus den Komponenten A), B), C) und D) in Gegenwart von F) und G), und gegebenenfalls der oder die Reaktiwerdünner (ii), gegebenenfalls gelöst in Aceton, werden unter starkem Rühren entweder in das Dispergierwasser, das das oder die Amine E) enthält, eingetragen oder man rührt umgekehrt die Dispergierwasser-Amin-Mischung zu der Polyurethanacrylatlösung. Außerdem bilden sich die Dispersionen aus, die im erfindungsgemäßen Beschichtungssystem enthalten sind. Die eingesetzte Menge an Amin E) hängt von den noch vorhandenen, nicht umgesetzten Isocyanatgruppen ab. Die Umsetzung der noch freien Isocyanatgruppen mit dem Amin E) kann zu 35% bis 150% erfolgen. In dem Fall, dass ein Unterschuss an Amin E) eingesetzt wird, reagieren noch freie Isocyanatgruppen langsam mit Wasser ab. Wird ein Überschuss an Amin E) verwendet, so liegen keine unreagierten Isocyanatgruppen mehr vor, und es wird ein aminfunktionelles Polyurethan erhalten. Bevorzugt werden 80% bis 110%, besonders bevorzugt 90% bis 100% der noch freien Isocyanatgruppen mit dem Amin E) umgesetzt.Subsequently, optionally, a reactive diluent (ii) or a mixture of reactive diluents (ii) may be added. The admixing of component (ii) is preferably carried out at 30 to 45 ° C. Once this has dissolved, optionally followed by the last reaction step in which take place in the aqueous medium, an increase in molecular weight and the formation of the dispersions required for the coating system according to the invention: The polyurethane acrylate (i), synthesized from the components A), B), C) and D) in the presence of F) and G), and optionally the reactive diluent (s) (ii), optionally dissolved in acetone, are added with vigorous stirring either into the dispersing water containing the amine (s) E) or, conversely, the mixture is stirred Dispersing water-amine mixture to the polyurethane acrylate solution. In addition, the dispersions formed in the coating system of the invention are formed. The amount of amine E) used depends on the remaining unreacted isocyanate groups. The reaction of the still free isocyanate groups with the amine E) can be carried out to 35% to 150%. In the event that a deficiency of amine E) is used, free isocyanate groups react slowly with water. When an excess of amine E) is used, unreacted isocyanate groups are no longer present and an amine-functional polyurethane is obtained. Preferably, 80% to 110%, particularly preferably 90% to 100% of the still free isocyanate groups are reacted with the amine E).
In einer weiteren Variante ist es möglich, die Molekulargewichtserhöhung durch das Amin E) bereits in acetonischer Lösung, d.h. vor der Dispergierung, und gegebenenfalls vor oder nach der Zugabe des oder der Reaktiwerdünner (ii) durchzuführen.In another variant, it is possible to increase the molecular weight of the amine E) already in acetonic solution, i. prior to dispersion, and optionally before or after the addition of the reactive diluent (s) (ii).
In einer weiteren Variante ist es möglich, die Molekulargewichtserhöhung durch das Amin E) nach dem Dispergierschritt durchzuführen.In a further variant, it is possible to carry out the molecular weight increase by the amine E) after the dispersing step.
Falls erwünscht, kann das organische Lösungsmittel - sofern vorhanden - abdestilliert werden. Die Dispersionen haben dann einen Festkörpergehalt von 20 bis 60 Gew.-%, insbesondere 30 bis 58 Gew.-%.If desired, the organic solvent, if present, can be distilled off. The dispersions then have a solids content of 20 to 60 wt .-%, in particular 30 to 58 wt .-%.
Es ist ebenfalls möglich, Dispergier- und Destillationsschritt parallel, das heißt gleichzeitig oder zumindest teilweise gleichzeitig durchzuführen.It is also possible to carry out the dispersion and distillation step in parallel, that is to say simultaneously or at least partly simultaneously.
Gegenstand der Erfindung ist auch die Verwendung der erfindungsgemäßen strahlenhärtbaren, wässrigen Dispersionen zur Herstellung von Beschichtungen insbesondere von Lacken und Klebstoffen.The invention also relates to the use of the radiation-curable, aqueous dispersions according to the invention for the production of coatings, in particular of paints and adhesives.
Die erfindungsgemäßen Dispersionen ergeben nach Entfernen des Wassers mit üblichen Methoden, wie Wärme, Wärmestrahlung, bewegter ggf. getrockneter Luft und / oder Mikrowellen, klare Filme. Durch anschließende strahlenchemisch und / oder radikalisch induzierte Vernetzung härten die Filme zu besonders hochwertigen und chemikalienresistenten Lacküberzügen aus.The dispersions according to the invention give clear films after removal of the water by customary methods, such as heat, heat radiation, moving optionally dried air and / or microwaves. Subsequent radiation-chemically and / or free-radically induced crosslinking, the films cure to form high-quality and chemical-resistant lacquer coatings.
Zur strahlenchemisch induzierten Polymerisation ist elektromagnetische Strahlung geeignet, deren Energie, gegebenenfalls unter Zusatz von geeigneten Photoinitiatoren, ausreicht, um eine radikalische Polymerisation von (Meth)acrylat-Doppelbindungen zu bewirken.For radiation-chemically induced polymerization, electromagnetic radiation is suitable whose energy, optionally with the addition of suitable photoinitiators, is sufficient to effect a radical polymerization of (meth) acrylate double bonds.
Bevorzugt erfolgt die strahlenchemisch induzierte Polymerisation mittels Strahlung mit einer Wellenlänge von kleiner 400 nm, wie UV-, Elektronen-, Röntgen- oder Gamma-Strahlen. Besonders bevorzugt ist die UV-Strahlung, wobei die Härtung mit UV-Strahlung in Gegenwart von Fotoinitiatoren ausgelöst wird. Bei den Fotoinitiatoren wird prinzipiell zwischen zwei Typen unterschieden, dem unimolekularen (Typ I) und dem bimolekularen (Typ II). Geeignete (Typ I)-Systeme sind aromatische Ketonverbindungen, wie z. B. Benzophenone in Kombination mit tertiären Aminen, Alkylbenzophenone, 4,4`-Bis(dimethylamino)benzophenon (Michlers Keton), Anthron und halogenierte Benzophenone oder Mischungen der genannten Typen. Weiter geeignet sind (Typ II)-Initiatoren wie Benzoin und seine Derivate, Benzilketale, Acylphosphinoxide, 2,4,6-Trimethyl-benzoyl-diphenylphosphinoxid, Bisacylphosphinoxide, Phenylglyoxylsäureester, Campherchinon, a-Aminoalkylphenone, a,a-Dialkoxyacetophenone und a-Hydroxyalkylphenone. Bevorzugt sind Fotoinitiatoren, die leicht in wässrige Beschichtungsmittel einzuarbeiten sind. Solche Produkte sind beispielsweise Irgacure® 500 (eine Mischung von Benzophenon und (1-Hydroxycyclohexyl)phenylketon, Fa. Ciba, Lampertheim, DE), Irgacure® 819 DW (Phenylbis-(2,4,6-trimethylbenzoyl)-phosphinoxid, Fa. Ciba, Lampertheim, DE), Esacure® KIP EM (Oligo-[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)-phenyl]-propanone], Fa. Lamberti, Aldizzate, Italien). Es können auch Gemische dieser Verbindungen eingesetzt werden.The radiation-induced polymerization preferably takes place by means of radiation having a wavelength of less than 400 nm, such as UV, electron, X-ray or gamma rays. Particularly preferred is the UV radiation, wherein the curing is initiated with UV radiation in the presence of photoinitiators. In the case of the photoinitiators, a distinction is in principle made between two types, the unimolecular (type I) and the bimolecular (type II). Suitable (Type I) systems are aromatic ketone compounds, such as. As benzophenones in combination with tertiary amines, alkylbenzophenones, 4,4'-bis (dimethylamino) benzophenone (Michler's ketone), anthrone and halogenated benzophenones or mixtures of the types mentioned. Also suitable are (type II) initiators such as benzoin and its derivatives, benzil ketals, acylphosphine oxides, 2,4,6-trimethyl-benzoyl-diphenylphosphine oxide, bisacylphosphine oxides, phenylglyoxylic acid esters, camphorquinone, α-aminoalkylphenones, α, α-dialkoxyacetophenones and α-hydroxyalkylphenones , Preference is given to photoinitiators which are easy to incorporate into aqueous coating compositions. Such products are, for example, Irgacure® 500 (a mixture of benzophenone and (1-hydroxycyclohexyl) phenylketone, Ciba, Lampertheim, DE), Irgacure® 819 DW (phenylbis- (2,4,6-trimethylbenzoyl) -phosphine oxide, Fa. Ciba, Lampertheim, DE), Esacure® KIP EM (Oligo- [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) -phenyl] -propanone], Lamberti, Aldizzate, Italy). It is also possible to use mixtures of these compounds.
Zur Einarbeitung der Photoinitiatoren können auch polare Lösemittel, wie z. B. Aceton und Isopropanol, verwendet werden.For incorporation of the photoinitiators and polar solvents, such as. As acetone and isopropanol can be used.
Vorteilhaft wird die UV-Härtung bei 30 bis 70 °C durchgeführt, weil bei höherer Temperatur der Umsetzungsgrad an (Meth)acrylatgruppen tendenziell erhöht ist. Dies kann bessere Beständigkeitseigenschaften zur Folge haben. Allerdings ist bei der UV-Härtung eine mögliche Temperaturempfindlichkeit des Substrats zu berücksichtigen, so dass optimale Härtungsbedingungen für eine bestimmte Beschichtungsmittel-Substrat-Kombination vom Fachmann in einfachen Vorversuchen zu ermitteln sind.Advantageously, the UV curing is carried out at 30 to 70 ° C, because at higher temperature, the degree of conversion of (meth) acrylate groups tends to increase. This can result in better resistance properties. However, in the case of UV curing, a possible temperature sensitivity of the substrate must be taken into account, so that optimum curing conditions for a particular coating agent-substrate combination by the expert in simple preliminary tests are to be determined.
Der oder die Strahler, die die radikalische Polymerisation auslösen, können dabei ortsfest sein und das beschichtete Substrat wird durch geeignete übliche Vorrichtungen am Strahler vorbeibewegt oder die Strahler sind durch übliche Vorrichtungen beweglich, so dass die beschichteten Substrate während der Härtung ortsfest sind. Es ist auch möglich die Bestrahlung z.B. in Kammern durchzuführen, bei denen das beschichtete Substrat in die Kammer eingebracht wird, anschließend die Strahlung für einen bestimmten Zeitraum eingeschaltet wird, und nach der Bestrahlung das Substrat wieder aus der Kammer entfernt wird.The radiator (s) which initiate the radical polymerization can be stationary and the coated substrate is moved past the radiator by means of suitable conventional devices, or the radiators are movable by conventional means, so that the coated substrates are stationary during curing. It is also possible to irradiate e.g. in chambers in which the coated substrate is introduced into the chamber, then the radiation is turned on for a certain period, and after the irradiation, the substrate is removed from the chamber again.
Gegebenenfalls wird unter Inertgasatmosphäre, d. h. unter Sauerstoffausschluss, gehärtet, um eine Inhibierung der radikalischen Vernetzung durch Sauerstoff zu verhindern.Optionally, under an inert gas atmosphere, i. H. oxygen-free, cured to prevent inhibition of free-radical cross-linking by oxygen.
Erfolgt die Härtung thermisch-radikalisch, eignen sich wasserlösliche Peroxide oder wässrige Emulsionen nicht-wasserlöslicher Initiatoren. Diese Radikalbildner können in bekannter Weise mit Beschleunigern kombiniert werden.If the curing takes place thermally-radically, water-soluble peroxides or aqueous emulsions of non-water-soluble initiators are suitable. These radical formers can be combined with accelerators in a known manner.
Die erfindungsgemäßen wässrigen, strahlenhärtbaren Polyurethandispersionen lassen sich durch die üblichen Techniken auf unterschiedlichste Substrate applizieren, bevorzugt Spritzen, Walzen, Fluten, Drucken, Rakeln, Gießen, Streichen und Tauchen.The aqueous, radiation-curable polyurethane dispersions according to the invention can be applied by the usual techniques to a wide variety of substrates, preferably spraying, rolling, flooding, printing, knife coating, casting, brushing and dipping.
Mit den erfindungsgemäßen wässrigen, strahlenhärtbaren Polyurethandispersionen können grundsätzlich alle Substrate lackiert bzw. beschichtet werden. Bevorzugte Substrate sind ausgewählt aus der Gruppe bestehend aus mineralischen Untergründen, Holz, Holzwerkstoffen, Möbeln, Parkett, Türen, Fensterrahmen, metallischen Gegenständen, Kunststoffen, Papier, Pappe, Kork, mineralischen Substraten, Textilien oder Leder. Sie eignen sich hierbei als Grundierung und / oder als Decklack. Zusätzlich können die erfindungsgemäßen wässrigen, strahlenhärtbaren Polyurethandispersionen auch in oder als Klebstoffe eingesetzt werden, z. B. in Kontaktklebstoffen, in thermoaktivierbaren Klebstoffen oder in Kaschierklebstoffen.With the aqueous, radiation-curable polyurethane dispersions according to the invention, basically all substrates can be coated or coated. Preferred substrates are selected from the group consisting of mineral substrates, wood, wood-based materials, furniture, parquet, doors, window frames, metallic objects, plastics, paper, cardboard, cork, mineral substrates, textiles or leather. They are suitable here as a primer and / or as a topcoat. In addition, the aqueous, radiation-curable polyurethane dispersions of the invention can also be used in or as adhesives, for. B. in contact adhesives, in thermally activated adhesives or in laminating adhesives.
Die erfindungsgemäßen wässrigen, strahlenhärtbaren Polyurethandispersionen können alleine aber auch in Bindemittelmischungen mit anderen Dispersionen eingesetzt werden. Dies können Dispersionen sein, die ebenfalls ungesättigte Gruppen enthalten, wie z. B. ungesättigte, polymerisierbare Gruppen enthaltende Dispersionen auf Polyester-, Polyurethan-, Polyepoxy(meth)acrylat-, Polyether-, Polyamid-, Polysiloxan-, Polycarbonat-, Epoxyacrylat-, Polyesteracrylat-, Polyurethan-Polyacrylat- und / oder Polyacrylatbasis.However, the aqueous, radiation-curable polyurethane dispersions according to the invention can also be used alone or in binder mixtures with other dispersions. These may be dispersions which also contain unsaturated groups, such as. B. unsaturated, polymerizable group-containing dispersions on polyester, polyurethane, polyepoxy (meth) acrylate, polyether, polyamide, polysiloxane, polycarbonate, Epoxyacrylat-, Polyesteracrylat-, polyurethane-polyacrylate and / or polyacrylate.
Es können auch solche Dispersionen auf Basis von Polyestern, Polyurethanen, Polyethern, Polyamiden, Polyvinylestern, Polyvinylethern, Polysiloxanen, Polycarbonaten, und / oder Polyacrylaten, in den erfindungsgemäßen Beschichtungssystemen enthalten sein, die funktionelle Gruppen, wie Alkoxysilangruppen, Hydroxygruppen und / oder gegebenenfalls in blockierter Form vorliegende Isocyanatgruppen aufweisen. So können Dual-Cure-Systeme hergestellt werden, die über zwei verschiedene Mechanismen ausgehärtet werden können.It is also possible to use dispersions based on polyesters, polyurethanes, polyethers, polyamides, polyvinyl esters, polyvinyl ethers, polysiloxanes, polycarbonates, and / or Polyacrylates to be contained in the coating systems of the invention, the functional groups such as alkoxysilane, hydroxy groups and / or optionally present in blocked form isocyanate groups. Thus, dual-cure systems can be produced, which can be cured by two different mechanisms.
Ebenfalls für Dual-Cure-Systeme können dem erfindungsgemäßen Beschichtungssystem, weiterhin so genannte Vernetzter zugesetzt werden. Es kommen bevorzugt nicht-blockierte und / oder blockierte Polyisocyanate, Polyaziridine, Polycarbodümide sowie Melaminharze in Frage. Besonders bevorzugt sind nicht-blockierte und / oder blockierte, hydrophilierte Polyisocyanate für wässrige Beschichtungsmittel. Bevorzugt werden <20 Gew.-%, besonders bevorzugt ≤10 Gew.-% an festem Vernetzer auf den Festgehalt des Beschichtungsmittels zugesetzt.Likewise for dual-cure systems, the so-called crosslinking agent can furthermore be added to the coating system according to the invention. Preference is given to non-blocked and / or blocked polyisocyanates, polyaziridines, polycarbodiimides and melamine resins. Non-blocked and / or blocked, hydrophilized polyisocyanates for aqueous coating compositions are particularly preferred. Preferably, < 20% by weight, more preferably ≦ 10% by weight, of solid crosslinking agent is added to the solids content of the coating composition.
Es können auch Dispersionen auf Basis von auf Polyestern, Polyurethanen, Polyethern, Polyamiden, Polysiloxanen, Polyvinylethern, Polybutadienen, Polyisoprenen, Chlorkautschuken, Polycarbonaten, Polyvinylestern, Polyvinylchloriden, Polyacrylaten, Polyurethan-Polyacrylat-, Polyesteracrylat-, Polyetheracrylat-, Alkyd-, Polycarbonat-, Polyepoxy-, Epoxy(meth)acrylatbasis in den erfindungsgemäßen Beschichtungssystemen enthalten sein, die keine funktionellen Gruppen aufweisen. Damit kann der Grad der Vernetzungsdichte reduziert werden, die physikalische Trocknung beeinflusst, z. B. beschleunigt werden, oder eine Elastifizierung bzw. auch eine Haftungsanpassung vorgenommen werden.It is also possible to use dispersions based on polyesters, polyurethanes, polyethers, polyamides, polysiloxanes, polyvinyl ethers, polybutadienes, polyisoprenes, chlorinated rubbers, polycarbonates, polyvinyl esters, polyvinyl chlorides, polyacrylates, polyurethane-polyacrylate, polyester acrylate, polyether acrylate, alkyd, polycarbonate Polyepoxy, epoxy (meth) acrylate-based be included in the coating systems of the invention which have no functional groups. This can reduce the degree of crosslink density which affects physical drying, e.g. B. be accelerated, or an elastification or a liability adjustment are made.
Den Beschichtungsmitteln, welche die erfindungsgemäßen wässrigen, strahlenhärtbaren Polyurethanacrylate enthalten, können auch Aminovernetzerharze, auf Melamin- oder Harnstoffbasis und / oder Polyisocyanate mit freien oder mit blockierten Polyisocyanatgruppen, auf Basis von gegebenenfalls hydrophilierenden Gruppen enthaltenden Polyisocyanaten aus Hexamethylendiisocyanat, Isophorondiisocyanat und / oder Toluylidendüsocyanat mit Urethan-, Uretdion-, Iminoxadiazindion-, Isocyanurat-, Biuret- und / oder Allophanatstrukturen zugesetzt sein. Als weitere Vernetzer sind auch Carbodiimide oder Polyaziridine möglich.The coating compositions which comprise the aqueous, radiation-curable polyurethane acrylates according to the invention may also be amino crosslinker resins, melamine- or urea-based and / or polyisocyanates with free or blocked polyisocyanate groups, based on optionally hydrophilicizing polyisocyanates of hexamethylene diisocyanate, isophorone diisocyanate and / or toluylene diisocyanate with urethane , Uretdione, iminoxadiazinedione, isocyanurate, biuret and / or allophanate structures. Carbodiimides or polyaziridines are also possible as further crosslinkers.
Die erfindungsgemäßen Beschichtunsmittel können mit den in der Lacktechnologie bekannten Bindemitteln, Hilfsstoffen und Additiven, wie z. B. Pigmente, Farbstoffe oder Mattierungsmittel versetzt bzw. kombiniert werden. Dies sind Verlaufs- und Benetzungsadditive, Slip-Additive, Pigmente einschließlich Metallic-Effektpigmente, Füllstoffe, Nanopartikel, Lichtschutzpartikel, Anti-Vergilbungsadditive, Verdicker und Additive zur Reduktion der Oberflächenspannung.The coating compositions according to the invention can with the known in paint technology binders, excipients and additives such. As pigments, dyes or matting agents are added or combined. These are leveling and wetting additives, slip additives, pigments including metallic effect pigments, fillers, nanoparticles, light protection particles, anti-yellowing additives, thickeners and surface tension reduction additives.
Die erfindungsgemäßen Beschichtungsmittel sind für die Beschichtungen von Folien geeignet, wobei zwischen physikalischer Trocknung und UV-Härtung eine Verformung der beschichteten Folie stattfindet.The coating compositions according to the invention are suitable for the coatings of films, wherein a deformation of the coated film takes place between physical drying and UV curing.
Besonders geeignet sind die erfindungsmäßigen Beschichtungsmittel für Klarlackanwendungen auf Holz- und Kunststoffsubstraten, bei denen es nach physikalischer Trocknung auf Blockfestigkeit und nach Strahlenhärtung auf gute Resistenzen gegen Chemikalien ankommt.Particularly suitable are the coating compositions according to the invention for clearcoat applications on wood and plastic substrates, which require good resistance to chemicals after physical drying for blocking resistance and after radiation curing.
Ebenfalls besonders geeignet sind die erfindungsmäßigen Beschichtungsmittel für Holz- und Kunststoffanwendungen mit einem Pigmentgehalt ≥10 Gew.-%, bezogen auf die gesamte Formulierung. Sollte es aufgrund von hohen Pigmentgehalten zu einer unvollständigen Reaktion der strahlungshärtbaren Gruppen im Beschichtungssystem während der Strahlungshärtung kommen, so werden blockfeste Beschichtungen erhalten.Also particularly suitable are the coating compositions according to the invention for wood and plastics applications with a pigment content ≥10% by weight, based on the total formulation. Should there be an incomplete reaction of the radiation-curable groups in the coating system during radiation curing due to high pigment contents, block-resistant coatings are obtained.
Beschichtungsmittel enthaltend die erfindungsgemäßen strahlenhärtbaren, wässrigen Dispersionen auf Polyurethanacrylatbasis, sowie Vernetzer auf Basis von Aminoharzen, blockierten Polyisocyanaten, nicht blockierten Polyisocyanaten, Polyaziridinen und / oder Polycarbodiimiden, und / oder ein oder mehrere weitere Dispersionen, sind ebenfalls Gegenstand der vorliegenden Erfindung.Coating compositions comprising the radiation-curable aqueous dispersions based on polyurethane acrylate according to the invention and also crosslinkers based on amino resins, blocked polyisocyanates, unblocked polyisocyanates, polyaziridines and / or polycarbodiimides, and / or one or more further dispersions are likewise provided by the present invention.
Weiterhin sind Substrate beschichtet mit den erfindungsgemäßen Beschichtungsmitteln ein Gegenstand dieser Erfindung.Furthermore, substrates coated with the coating compositions of the invention are an object of this invention.
Methoden:
Die Bestimmung der Gewichtsmittel des Molekulargewichts Mw der Polyurethanacrylate mittels Gelpermeationschromatographie erfolgte auf folgendem System:
Der Feststoffgehalt der Polyurethandispersion wurde gravimetrisch nach Abdampfen aller nichtflüchtigen Bestandteile gemäß DIN 53216 bestimmt.methods:
The determination of the weight-average molecular weight M w of the polyurethane acrylates by means of gel permeation chromatography was carried out on the following system:
The solids content of the polyurethane dispersion was determined gravimetrically after evaporation of all nonvolatile constituents in accordance with DIN 53216.
Die mittlere Teilchengröße wurde durch Laser-Korrelationsspektroskopie ermittelt.The mean particle size was determined by laser correlation spectroscopy.
Die Auslaufzeit wurde gemäß DIN 53211 mit Hilfe des 4 mm DIN-Bechers bestimmt.The flow time was determined in accordance with DIN 53211 using the 4 mm DIN cup.
Um die Lagerstabilität einer wässrigen, strahlenhärtbaren Polyurethandispersion zu bestimmen, wurde eine Probe über 7 Tage bei 40 °C gelagert und anschließend auf Sedimentation, Koagulation oder Serumbildung begutachtet. Die Probe war lagerstabil (i. 0.), wenn nach Lagerung optisch keine Veränderungen festgestellt wurden.To determine the storage stability of an aqueous, radiation-curable polyurethane dispersion, a sample was stored for 7 days at 40 ° C and then examined for sedimentation, coagulation or serum formation. The sample was stable on storage (i.o.) when no changes were observed after storage.
Katalysatoren zur Synthese der wässrigen, strahlenhärtbare Polyurethandispersionen:
- Desmorapid Z: Dibutylzinndilaurat der Fa. Bayer MaterialScience AG, Leverkusen, DE
- Desmorapid SO: Zinn(II)-2-ethylhexanoat der Fa. Bayer MaterialScience AG, Leverkusen, DE
- Borchikat 24: Bismuth(III)-2-ethylhexanoat der Fa. Borchers GmbH, Langenfeld, DE
- Borchikat 22: Zink(II)-2-ethylhexanoat der Fa. Borchers GmbH, Langenfeld, DE
- VEXP 0519: Titan(IV)katalysator für 2K-Anwendung der Fa. Johnson Matthey, London, England
- VEXP 0588: Zirkonium(IV)katalysator für 2K-Anwendungen der Fa. Johnson Matthey, London, England
- VEXP 0584: Zirkonium(IV)katalysator für 2K-Anwendungen der Fa. Johnson Matthey, London, England
- Desmorapid Z: dibutyltin dilaurate from Bayer MaterialScience AG, Leverkusen, DE
- Desmorapid SO: tin (II) 2-ethylhexanoate from Bayer MaterialScience AG, Leverkusen, DE
- Borchicate 24: Bismuth (III) 2-ethylhexanoate from Borchers GmbH, Langenfeld, DE
- Borchicate 22: Zinc (II) 2-ethylhexanoate from Borchers GmbH, Langenfeld, DE
- VEXP 0519: Titan (IV) catalyst for 2K application from Johnson Matthey, London, England
- VEXP 0588: zirconium (IV) catalyst for 2K applications from Johnson Matthey, London, England
- VEXP 0584: zirconium (IV) catalyst for 2K applications from Johnson Matthey, London, England
Verwendete Abkürzungen:
- FG: Festgehalt, MTG: mittlere Teilchengröße, ALZ: Auslaufzeit, Mw: Gewichtsmittel des Molekulargewichts, i.O.: in Ordnung, n.b.: nicht bestimmt
- FG: fixed content, MTG: mean particle size, ALZ: flow time, M w : weight average molecular weight, OK: in order, nb: not determined
400,6 Teile des Polyesteracrylats Laromer® PE 44 F (BASF AG, Ludwigshafen, DE), Komponente A), 5,4 Teile Hexandiol, Komponente B), 34,0 Teile Dimethylolpropionsäure, , Komponente C), 77,2 Teile Hexamethylendiisocyanat, Komponente D), 66,6 Teile 1-Isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexan, Komponente D), und 0,63 Teile (1,0 mmol) Desmorapid Z (Dibutylzinndilaurat der Fa. Bayer MaterialScience AG, Leverkusen, DE) wurden in 190 Teilen Aceton gelöst und bis zu einem NCO-Gehalt von 1,7 Gew.-% (Theorie 1,7 Gew.-%) bei 60 °C unter Rühren umgesetzt. Anschließend erfolgte die Neutralisation durch Zugabe und Unterrühren von 20,2 Teilen Triethylamin. Die klare Lösung wurde unter Rühren in 950 Teilen Wasser eingetragen. Daraufhin wurde eine Mischung aus 8,4 Teilen Ethylendiamin, Komponente E, und 24,0 Teilen Wasser der Dispersion unter Rühren zugesetzt. Im Anschluss wurde das Aceton unter leichtem Vakuum aus der Dispersion abdestilliert. Es wurde eine UV-härtbare, wässrige Polyurethan-Dispersion 1) mit einem Feststoffgehalt (FG) von 39,8 Gew.-%, einer Auslaufzeit (ALZ) von 24 sec, einer mittleren Teilchengröße (MTG) von 80 nm und einem pH-Wert von 8,4 erhalten. Das Gelpermeationschromatogramm zeigte ein Gewichtsmittel des Molekulargewichts Mw für das dispergierte Polyurethanacrylat von 2,00*105 g/mol.400.6 parts of the polyester acrylate Laromer ® PE 44 F (BASF AG, Ludwigshafen, DE), component A), 5.4 parts of hexanediol, component B), 34.0 parts of dimethylolpropionic acid, component C), 77.2 parts of hexamethylene diisocyanate , Component D), 66.6 parts of 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, component D), and 0.63 parts (1.0 mmol) of Desmorapid Z (dibutyltin dilaurate from Bayer MaterialScience AG , Leverkusen, DE) were dissolved in 190 parts of acetone and reacted to an NCO content of 1.7 wt .-% (theory 1.7 wt .-%) at 60 ° C with stirring. Subsequently, the neutralization was carried out by adding and stirring in of 20.2 parts of triethylamine. The clear solution was added with stirring in 950 parts of water. Thereafter, a mixture of 8.4 parts of ethylenediamine, Component E, and 24.0 parts of water was added to the dispersion with stirring. Subsequently, the acetone was distilled off under slight vacuum from the dispersion. A UV-curable, aqueous polyurethane dispersion 1) having a solids content (FG) of 39.8% by weight, a flow time (ALZ) of 24 sec, an average particle size (MTG) of 80 nm and a pH Value of 8.4 received. The gel permeation chromatogram showed a weight average molecular weight M w for the dispersed polyurethane acrylate of 2.00 * 10 5 g / mol.
Die folgenden Beispiele 2) bis 18) wurden analog zu Beispiel 1) allerdings mit anderen Katalysatoren und ggf. mit Zusatz von Säure durchgeführt.
Die Beispiele 2) bis 8) zeigen, dass alternative Urethanisierungskatalysatoren, wie sie aus 2K-Anwendungen bekannt sind, nicht geeignet sind, DBTL in Beispiel 1) zu ersetzen. Dazu zählt auch Bismuth(III)-2-ethylhexanoat, Beispiel 2). Beispiele 2), 3), 5) und 8) wiesen im Vergleich zu Beispiel 1) allesamt ein niedrigeres Gewichtsmittel des Molekulargewichts Mw, demzufolge eine größere MTG und gegebenenfalls eine unzureichende Lagerstabilität bei erhöhter Temperatur auf. Die Beispiele 4), 6) und 7) waren recht hochviskos und nicht sonderlich feinteilig und reichten nicht an die Qualität von Beispiel 1) heran.
Die erfindungsgemäßen Beispiele 9) bis 12) zeigen, dass die Kombination von Bismuth(III)-2-ethylhexanoat und der starken Säure Phosphorsäure-di-(n-butyl)ester in Bezug auf MTG, ALZ und Mw zu mit Beispiel 1) vergleichbaren Ergebnissen kommt. Die erfindungsgemäßen Beispiele 9) bis 12) zeigen, dass bei gleichbleibender Menge an Bismuthsalz und steigender Menge an Säure das Gewichtsmittel des Molekulargewichts Mw des Polyurethanacrylates und die Feinteiligkeit der wässrigen, strahlenhärtbaren Polyurethandispersion zunehmen und bei äquimolaren Mengen an Bismuthsalz und Säure ihr Maximum erreichen. Bei einem Überschuss Säure, im Vergleich zum Bismuthsalz, nimmt das Gewichtsmittel des Molekulargewichts Mw wieder ab.
Die erfindungsgemäßen Beispiele 13) bis 15) zeigen, dass auch andere Bismuth(III)salze und andere starke Säuren den gleichen Effekt zeigen wie Beispiel 9).
Die Beispiele 16) bis 18) zeigen, dass der Zusatz einer starken Säure zu Zinn(II)-2-ethylhexanoat nicht den gleichen Effekt aufweist wie in den Beispielen 9) bis 11). Die Ergebnisse zeigen sogar, dass mit steigender Menge Säure das Gewichtsmittel des Molekulargewichts Mw abnimmt.Examples 16) to 18) show that the addition of a strong acid to stannous 2-ethylhexanoate does not have the same effect as in Examples 9) to 11). The results even show that as the amount of acid increases, the weight average molecular weight M w decreases.
6574 Teile Isophthalsäure, 1327 Teile Trimethylolpropan, 7207 Teile Neopentylglykol und 4 Teile Fascat® 4100 (Butylstannonsäure, Arcema Inc., Philadelphia, PA, US) wurden gemeinsam unter Rühren auf 190 °C aufgeheizt. Diese Temperatur wurde gehalten, bis eine Säurezahl von weniger als 1,5 mg KOH/g Substanz erreicht war. Es wurde ein Polyester mit einer mittleren Funktionalität von 2,3 und einer Hydroxylzahl von 365 mg KOH/g Substanz erhalten.6574 parts of isophthalic acid, 1,327 parts of trimethylolpropane, 7207 parts of neopentyl glycol and 4 parts of Fascat ® 4100 (butylstannonic acid, Arcema Inc., Philadelphia, PA, US) were heated together with stirring to 190 ° C. This temperature was maintained until an acid number of less than 1.5 mg KOH / gm of substance was achieved. A polyester having an average functionality of 2.3 and a hydroxyl number of 365 mg KOH / g substance was obtained.
Bei 60 °C wurden zu einer Mischung von 2236 Teilen 4,4'-Diisocyanatodicyclohexylmethan, Komponente D, 2244 Teilen DesmodurⓇ N 3300 (HDI-Trimerisat, Bayer AG, Leverkusen, DE), Komponente D und 0,75 Teilen Dibutylzinndilaurat in 1519 Teilen Aceton 1595 Teile 2-Hydroxyethylacrylat, Komponente A, zudosiert und weiter bei 60 °C verrührt bis ein NCO-Gehalt von 8,2 Gew.-% erreicht wurde. Anschließend wurden bei 40 °C 1373 Teile des Polyesters aus Beispiel 19), Komponente B, gelöst in 421 Teilen Aceton, 305 Teile Dimethylolpropionsäure, Komponente C, und 0,75 Teile DBTL (1,18 mmol) zugegeben und die Mischung auf 60 °C unter Rühren aufgeheizt. Nach Erreichen eines NCO-Gehaltes von 0,6 Gew.-% wurde auf 40 °C abgekühlt, und es folgte die Neutralisation mit 147 Teilen Triethylamin. Die klare Lösung wurde unter Rühren in 11350 Teile Wasser eingetragen. Daraufhin wurde eine Mischung aus 43,6 Teilen Ethylendiamin, Komponente E, und 100 Teilen Wasser der Dispersion unter Rühren zugesetzt. Im Anschluss wurde das Aceton unter leichtem Vakuum aus der Dispersion abdestilliert. Man erhielt eine UV-härtbare, wässrige Polyurethan-Dispersion 20) mit einem Feststoffgehalt von 43 Gew.-%, einer mittleren Teilchengröße von 132 nm und einem pH-Wert von 8,0. Das Gelpermeationschromatogramm der Dispersion zeigte ein Gewichtsmittel des Molekulargewichts Mw von 1,68*104 g/mol.At 60 ° C were added to a mixture of 2236 parts of 4,4'-diisocyanatodicyclohexylmethane, component D, 2244 parts Desmodur Ⓡ N 3300 (HDI trimer , Bayer AG, Leverkusen, DE), component D and 0.75 parts of dibutyltin dilaurate in 1519 Add acetone 1595 parts of 2-hydroxyethyl acrylate, component A, metered in and further stirred at 60 ° C until an NCO content of 8.2 wt .-% was achieved. Subsequently, at 40 ° C., 1373 parts of the polyester from example 19), component B, dissolved in 421 parts of acetone, 305 parts of dimethylolpropionic acid, component C, and 0.75 part of DBTL (1.18 mmol) were added and the mixture was brought to 60.degree C heated with stirring. After reaching an NCO content of 0.6 wt .-% was cooled to 40 ° C, and it was followed by neutralization with 147 parts of triethylamine. The clear solution was added with stirring to 11350 parts of water. Subsequently, a mixture of 43.6 parts of ethylenediamine, Component E, and 100 parts of water was added to the dispersion with stirring. Subsequently, the acetone was distilled off under slight vacuum from the dispersion. This gave a UV-curable, aqueous polyurethane dispersion 20) having a solids content of 43 wt .-%, an average particle size of 132 nm and a pH of 8.0. The gel permeation chromatogram of the dispersion showed a weight average molecular weight M w of 1.68 * 10 4 g / mol.
Die Herstellung verlief gemäß Beispiel 20), allerdings wurden statt DBTL 0,76 Teile Borchikat 24 (1,18 mmol) und 0,25 Teile Phosphorsäure-di-(n-butyl)ester (1,18 mmol) verwendet. Man erhielt eine UV-härtbare, wässrige Polyurethan-Dispersion 21) mit einem Feststoffgehalt von 42 Gew.-%, einer mittleren Teilchengröße von 114 nm und einem pH-Wert von 8,7. Das Gelpermeationschromatogramm zeigte ein Gewichtsmittel des Molekulargewichts Mw von 1,93*104 g/mol.The preparation proceeded in accordance with Example 20), but instead of DBTL, 0.76 part of borochate 24 (1.18 mmol) and 0.25 part of di (n-butyl) phosphoric acid (1.18 mmol) were used. A UV-curable, aqueous polyurethane dispersion 21) having a solids content of 42% by weight, an average particle size of 114 nm and a pH of 8.7 was obtained. The gel permeation chromatogram showed a weight average molecular weight Mw of 1.93 * 10 4 g / mol.
468 g Desmodur N 3300 (Trimer mit Isocyanuratstruktureinheiten auf Basis von Hexamethylendiisocyanat, Bayer MaterialScience, Deutschland), Komponente D, 2,6 g Neopentylglykol, Komponente B, 34,8 g Dimethylolpropionsäure, Komponente C, 0,40 g DBTL (0,60 mmol) und 0,4 g 2,6-Di-tert-butyl-4-methylphenol (Inhibitor KBⓇ) wurden in 300 g Aceton gelöst und homogenisiert. Bei 55 °C wurden 204,2 g Hydroxyethylacrylat, Komponente A, so zudosiert, dass die Temperatur nicht über 65 °C stieg. Nach Erreichen des theoretischen NCO-Wertes von 0,3 Gew.-% wurde eine Lösung von 3,0 g Ethylendiamin, Komponente E, in 32 g Aceton zugegeben und 30 Minuten gerührt. Nach Zugabe von 19 g Triethylamin wurden 980 g destilliertes Wasser zum Dispergieren zugegeben und das Aceton im leichten Vakuum abdestilliert. Man erhielt eine UV-härtbare, wässrige Polyurethan-Dispersion 22) mit einem Feststoffgehalt von 37%, einem pH-Wert von 7,9 und einer mittleren Teilchengröße von 97 nm. Das Gelpermeationschromatogramm zeigte ein Gewichtsmittel des Molekulargewichts Mw von 3,43*103 g/mol.468 g Desmodur N 3300 (trimer with isocyanurate structural units based on hexamethylene diisocyanate, Bayer MaterialScience, Germany), component D, 2.6 g neopentyl glycol, component B, 34.8 g dimethylolpropionic acid, component C, 0.40 g DBTL (0.60 mmol) and 0.4 g of 2,6-di-tert-butyl-4-methylphenol (inhibitor KB Ⓡ ) were dissolved in 300 g of acetone and homogenized. At 55 ° C, 204.2 g of hydroxyethyl acrylate, component A, were metered in so that the temperature did not rise above 65 ° C. After reaching the theoretical NCO value of 0.3 wt .-%, a solution of 3.0 g of ethylenediamine, component E, in 32 g of acetone was added and stirred for 30 minutes. After adding 19 g of triethylamine, 980 g of distilled water were added to disperse and the acetone was distilled off in a slight vacuum. This gave a UV-curable, aqueous polyurethane dispersion 22) having a solids content of 37%, a pH of 7.9 and an average particle size of 97 nm. The gel permeation chromatogram showed a weight average molecular weight Mw of 3.43 * 10 3 g / mol.
Die Herstellung verlief gemäß Beispiel 22), allerdings wurden statt DBTL 0,40 Teile Borchikat 24 (0,60 mmol) und 0,13 Teile Phosphorsäure-di-(n-butyl)ester (0,60 mmol) verwendet. Man erhielt eine UV-härtbare, wässrige Polyurethan-Dispersion 23) mit einem Feststoffgehalt von 39 Gew.-%, einer mittleren Teilchengröße von 103 nm und einem pH-Wert von 8,2. Das Gelpermeationschromatogramm zeigte ein Gewichtsmittel des Molekulargewichts Mw von 3,31*103 g/mol.The preparation proceeded according to Example 22), but instead of DBTL 0.40 parts of borochate 24 (0.60 mmol) and 0.13 part of phosphoric acid di (n-butyl) ester (0.60 mmol) were used. A UV-curable, aqueous polyurethane dispersion 23) having a solids content of 39% by weight, an average particle size of 103 nm and a pH of 8.2 was obtained. The gel permeation chromatogram showed a weight average molecular weight M w of 3.31 * 10 3 g / mol.
Die Beispiele 21) und 23) zeigen im Vergleich zu den Beispielen 20) und 22), dass mit der Kombination Bismuth(III)-2-ethylhexanoat und Phosphorsäure-di-(n-butyl)ester nahezu gleiche wässrige, strahlenhärtbare Polyurethandispersionen synthetisiert werden können wie unter DBTL-Katalyse.Examples 21) and 23) show that the combination of bismuth (III) 2-ethylhexanoate and di (n-butyl) phosphoric acid ester synthesizes almost identical aqueous, radiation-curable polyurethane dispersions in comparison to Examples 20) and 22) can as under DBTL catalysis.
Nach der UV-Härtung werden die beschichteten Substrate gelagert (Glas 1 h bei Raumtemperatur im Exsikkator) und anschließend den Prüfungen unterzogen.
- 1 eine Mischung von Benzophenon und (1-Hydroxycyclohexyl)phenylketon der Fa. Ciba, Lampertheim, DE
- 2 Lösung eines polyethermodifizierten Polydimethylsiloxans der Fa. BYK, Wesel, DE
- 3 Lösung eines harnstoffmodifizierten Polyurethans der Fa. BYK, Wesel, DE
- 4 Zum Test der Reaktivität wird die nach der Aushärtung erzielte Härte in Pendelsekunden (nach DIN 53157) in Abhängigkeit von verschiedenen Bandlaufgeschwindigkeiten gemessen. Bleibt die Pendelhärte auch bei höchster Bandgeschwindigkeit bei Werten über 100 Pendelsekunden, so besitzt die Beschichtung eine ausgezeichnete Reaktivität.
- 5 UV-Anlage der Fa. Barberän, Model HOK - 6/2 (ca. 80 W/cm)
- 1 a mixture of benzophenone and (1-hydroxycyclohexyl) phenyl ketone from Ciba, Lampertheim, DE
- 2 Solution of a polyether-modified polydimethylsiloxane Fa. BYK, Wesel, DE
- 3 solution of a urea-modified polyurethane from. BYK, Wesel, DE
- 4 To test the reactivity, the hardness achieved after curing in pendulum seconds (according to DIN 53157) is dependent on different belt speeds measured. If the pendulum hardness remains above 100 pendulum seconds even at maximum belt speed, the coating has excellent reactivity.
- 5 UV system from Barberän, model HOK - 6/2 (about 80 W / cm)
Daten zur anwendungstechnischen Prüfung von Klarlacksystemen
Note 5: klar, keine Trübung oder Schleierbildung erkennbar
Note 4: bei einem Betrachtungswinkel von ca. 10 bis 20 ° ist eine leichte Schleierbildung erkennbar
Note 3: bei einem Betrachtungswinkel von ca. 45 bis 80 ° ist eine leichte Trübung erkennbar
Note 2: deutliche Trübung
Note 1: matte Oberfläche bzw. griesige Oberfläche
Grade 5: clear, no haze or haze visible
Grade 4: at a viewing angle of approx. 10 to 20 °, a slight fog is visible
Grade 3: at a viewing angle of approx. 45 to 80 °, a slight haze is visible
Grade 2: significant haze
Grade 1: matte surface or gritty surface
Die Beständigkeitseigenschaften werden nach 16 Stunden Belastung durch optische Inaugenscheinnahme beurteilt:
- Note 5: Keine sichtbaren Veränderungen (keine Beschädigung).
- Note 4: Leichte Glanz- oder Farbtonveränderung, nur sichtbar, wenn sich die Lichtquelle in der Prüfoberfläche auf oder dicht neben der Markierung spiegelt und direkt zum Auge des Betrachters reflektiert wird, oder einige eben erkennbare, abgegrenzte Markierungen (Quellungsring erkennbar, bzw. keine Erweichung mit dem Fingernagel erkennbar).
- Note 3: Leichte Markierung aus mehreren Blickwinkeln zu sehen, zum Beispiel ein eben erkennbarer fast völliger Kreis oder Kreisfläche (Quellungsring erkennbar, Kratzspuren des Fingernagels erkennbar)
- Note 2: Starke Markierung, die Oberflächenstruktur ist jedoch weitgehend unverändert. (geschlossener Quellungsring, Kratzspuren feststellbar).
- Note 1: Starke Markierung, die Oberflächenstruktur ist jedoch weitgehend unverändert, Markierung ist bis zum Untergrund durchkratzbar
- Note 0: Starke Markierung, die Oberflächenstruktur ist verändert oder das Oberflächenmaterial ist ganz oder teilweise zerstört oder das Filterpapier haftet an der Oberfläche.
- 8 Das Weissanlaufen nach Verkratzung wird durch Verkratzen mittels einer Münze geprüft. Ist an der Verkratzungsstelle keinerlei Weissanlaufen erkennbar, dann wird dieses Ergebnis als exzellent beurteilt (Note 5).
- Grade 5: No visible changes (no damage).
- Grade 4: Slight change in gloss or hue, only visible if the light source in the test surface is reflected on or close to the mark and reflected directly to the observer's eye, or if there are some identifiable delimited markings (swelling ring visible, or no softening recognizable with the fingernail).
- Grade 3: Easy to see from several angles, for example, a just recognizable almost complete circle or circular area (swelling ring visible, scratch marks of the fingernail recognizable)
- Grade 2: Strong marking, but the surface structure is largely unchanged. (closed swelling ring, scratch marks detectable).
- Grade 1: Strong marking, but the surface structure is largely unchanged, marking is scratched to the ground
- Grade 0: Strong marking, the surface structure is changed or the surface material is completely or partially destroyed or the filter paper adheres to the surface.
- 8 Scratching after scratching is checked by scratching with a coin. If there is no discernible blush at the scratch site, then this result is considered excellent (rating 5).
Die anwendungstechnische Prüfung der Bindemittel aus den Beispielen 9, 10 und 11 im Klarlack zeigt, dass in Relation zum Klarlack, hergestellt aus dem DBTL-katalysierten Bindemittel von Beispiel 1, gleich gute Ergebnisse erreicht werden.The performance testing of the binders of Examples 9, 10 and 11 in the clearcoat shows that in relation to the clearcoat prepared from the DBTL-catalyzed binder of Example 1, equally good results are achieved.
Claims (15)
enthält, die in Gegenwart von
contains, in the presence of
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PL10188971T PL2316867T3 (en) | 2009-10-31 | 2010-10-27 | Tin-free, aqueous polyurethane dispersions |
SI201030052T SI2316867T1 (en) | 2009-10-31 | 2010-10-27 | Tin-free, aqueous polyurethane dispersions |
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---|---|---|---|
DE102009051557 | 2009-10-31 |
Publications (2)
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EP2316867A1 true EP2316867A1 (en) | 2011-05-04 |
EP2316867B1 EP2316867B1 (en) | 2012-05-09 |
Family
ID=43446376
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EP10188971A Active EP2316867B1 (en) | 2009-10-31 | 2010-10-27 | Tin-free, aqueous polyurethane dispersions |
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US (1) | US8865832B2 (en) |
EP (1) | EP2316867B1 (en) |
JP (1) | JP5602587B2 (en) |
KR (1) | KR101782162B1 (en) |
CN (1) | CN102051040B (en) |
AT (1) | ATE557051T1 (en) |
BR (1) | BRPI1004096A2 (en) |
CA (1) | CA2719227C (en) |
DK (1) | DK2316867T3 (en) |
ES (1) | ES2385441T3 (en) |
HK (1) | HK1152541A1 (en) |
HR (1) | HRP20120642T1 (en) |
PL (1) | PL2316867T3 (en) |
SI (1) | SI2316867T1 (en) |
TW (1) | TWI501987B (en) |
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WO2015055591A1 (en) | 2013-10-16 | 2015-04-23 | Basf Se | Process for preparing water-emulsifiable polyurethane acrylates |
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WO2016096503A1 (en) | 2014-12-17 | 2016-06-23 | Basf Se | Radiation curable coating composition based on chain-extended and cross-linked polyurethanes |
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US10131814B2 (en) | 2013-08-26 | 2018-11-20 | Basf Se | Radiation-curable water-dispersible polyurethane (meth)acrylates |
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Cited By (15)
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WO2014063920A1 (en) | 2012-10-24 | 2014-05-01 | Basf Se | Radiation-curing, water-dispersible polyurethane (meth)acrylates |
US9752056B2 (en) | 2012-10-24 | 2017-09-05 | Basf Se | Radiation-curing, water-dispersible polyurethane (meth)acrylates |
US9738597B2 (en) | 2013-05-27 | 2017-08-22 | Basf Se | Method for preparing urethane (meth)acrylates |
US10131814B2 (en) | 2013-08-26 | 2018-11-20 | Basf Se | Radiation-curable water-dispersible polyurethane (meth)acrylates |
WO2015055591A1 (en) | 2013-10-16 | 2015-04-23 | Basf Se | Process for preparing water-emulsifiable polyurethane acrylates |
US10294392B2 (en) | 2013-10-16 | 2019-05-21 | Basf Se | Process for preparing water-emulsifiable polyurethane acrylates |
US9340704B2 (en) | 2014-04-08 | 2016-05-17 | Dymax Corporation | Sunlight curable coating compositions |
EP2930199A1 (en) * | 2014-04-08 | 2015-10-14 | Dymax Corporation | Sunlight curable coating compositions |
RU2669612C2 (en) * | 2014-04-18 | 2018-10-12 | Таркетт Гдл | Polyurethane coating, which is cured using the actinic radiation for decorative lining coatings |
WO2016096503A1 (en) | 2014-12-17 | 2016-06-23 | Basf Se | Radiation curable coating composition based on chain-extended and cross-linked polyurethanes |
US10584262B2 (en) | 2014-12-17 | 2020-03-10 | Basf Se | Radiation curable coating composition based on chain-extended and cross-linked polyurethanes |
US10703929B2 (en) | 2015-08-17 | 2020-07-07 | Basf Se | Aqueous polymer compositions comprising polyurethane (meth)acrylates |
WO2017102777A1 (en) | 2015-12-15 | 2017-06-22 | Basf Se | Aqueous polymer dispersion for adhesive compounds |
WO2020012039A1 (en) | 2018-07-13 | 2020-01-16 | Miwon Austria Forschung Und Entwicklung Gmbh | Water-dispersible polyurethane (meth)acrylates for actinic radiation curable coatings |
US12065532B2 (en) | 2018-07-13 | 2024-08-20 | Miwon Austria Forschung Und Entwicklung Gmbh | Water-dispersible polyurethane (meth)acrylates for actinic radiation curable coatings |
Also Published As
Publication number | Publication date |
---|---|
US8865832B2 (en) | 2014-10-21 |
JP5602587B2 (en) | 2014-10-08 |
HK1152541A1 (en) | 2012-03-02 |
KR101782162B1 (en) | 2017-09-26 |
ATE557051T1 (en) | 2012-05-15 |
TW201120079A (en) | 2011-06-16 |
BRPI1004096A2 (en) | 2012-07-24 |
PL2316867T3 (en) | 2012-09-28 |
KR20110047997A (en) | 2011-05-09 |
SI2316867T1 (en) | 2012-09-28 |
DK2316867T3 (en) | 2012-08-27 |
JP2011094141A (en) | 2011-05-12 |
US20120041131A1 (en) | 2012-02-16 |
CA2719227C (en) | 2017-01-10 |
TWI501987B (en) | 2015-10-01 |
ES2385441T3 (en) | 2012-07-24 |
HRP20120642T1 (en) | 2012-10-31 |
CN102051040B (en) | 2014-06-25 |
CN102051040A (en) | 2011-05-11 |
EP2316867B1 (en) | 2012-05-09 |
CA2719227A1 (en) | 2011-04-30 |
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